Odorous compounds and method of preparation thereof

Abstract

The present invention relates to odorous compounds denoted by formula (I), which are useful as fragrance or flavor materials in particular in providing lily-of-the-valley (muguet) along with geranium, melonal, floral, and / or aldehydic 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). 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] 09545(2) 1

[0002] ODOROUS COMPOUNDS AND METHOD OF PREPARATION THEREOF

[0003] FIELD OF THE INVENTION

[0004] The present invention relates to odorous compounds denoted by formula (I) which are useful as fragrance or flavor materials in particular in providing lily-of-the-valley (muguet), geranium, melonal, floral, and / or aldehydic 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). 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.

[0005] BACKGROUND OF THE INVENTION

[0006] There is huge demand for odorants that impart lily-of-the-valley (muguet), geranium, melonal, floral, and / or aldehydic type notes to perfume, aroma or deodorizing / masking compositions. It is estimated that 20% of odorants in the total perfumery raw materials market is captured by lily-of-the-valley odorants. Lily-of-the-valley odor comprises of green and floral scent, often with fresh and sweet notes. Cyclamen Aldehyde® is one of the earliest examples of synthetic lily-of-the-valley odorants. Designs of Lilial® and Bourgeonal® were inspired by Cyclamen Aldehyde®. Lilial® was used from 1946 extensively in all categories such as fine fragrances, shampoos, detergents, toiletries and household cleaners. However, after studies indicated reproductive toxicity effects in male rats, Lilial® was classified as CMR 2 and eventually from March 2022 Lilial® has been banned from use in cosmetic products. Detailed experimental studies indicates that p-tertiary-butyl benzoic acid, a metabolite of Lilial® is responsible for the toxic effects in rats.

[0007] Many fragrance companies initiated research programs for discovery of safer alternatives to Lilial®. This led to the discovery of many aromatic as well as non-aromatic lily-of-the-valley odorants. Notable examples of such aromatic lily-of-the-valley odorants are Florhydral®, Mimosal® and Nympheal®. A methyl group strategically placed ortho to the 3 -carbon chain in Nympheal® is said to be responsible for elimination of toxicity to rats.

[0008] Some of the non-aromatic lily-of-the-valley odorants are Florol® and Mahonial®. 09545(2) 2

[0009] Regulatory agencies are ever more stringent on the introduction of novel odorants for use in cosmetic products. 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.

[0010] Therefore, novel compounds that possess lily-of-the-valley (muguet) profile along with geranium, melonal, floral, and / or aldehydic aspects have high demand in the perfumery market.

[0011] It is an advantage of the present invention that odorous compounds denoted by formula (I) are useful as fragrance or flavor materials, in particular in providing lily-of-the-valley (muguet) profile along with geranium, melonal, floral, and / or aldehydic type notes to perfume, aroma or deodorizing / masking compositions.

[0012] The present invention also relates to a process for preparation of odorous compounds of formula (I).

[0013] INVENTION

[0014] This invention discloses fragrance, flavor and / or deodorizing / masking compositions comprising compounds of formula (I). Here the compounds of formula (I) can be any one of its stereoisomers or a mixture of one or more of these stereoisomers. Further, compounds of formula (I) can be one of its regioisomers or a mixture of one or more of its regioisomers.

[0015] The invention further discloses odorous compounds of formula (I) per se, as well as its stereoisomers or a mixture thereof and / or regioisomers or a mixture thereof.

[0016] Particularly, the invention discloses fragrance, flavor and / or deodorizing / masking compounds of formula (I)

[0017] ■2

[0018]

[0019] R3Me R

[0020] Formula (I)

[0021] wherein 09545(2) 3

[0022] X is selected from -CH2OH, -CHO, -CN, -COOMe, -COOEt;

[0023] Ri, R2 and R3 can be any of the groups from H, Me, Et, n-Pr, i-Pr;

[0024] R4 and R5 can be independently any of the groups from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, tertiary butyl, 2-butyl (sec-butyl), n-pentyl, n-hexyl, n-heptyl, 3 -ethyl-3 -pentyl, n-octyl, methylidene, ethylidene, propylidene, isopropylidene, 2-methylpropylidene, butylidene, 2-butylidene, pentylidene, hexylidene, heptylidene, octylidene; and

[0025] dotted line can be single bond or double bond.

[0026] In an embodiment, R4 and R5 can’t be both an alkylidene in a formula (I) compound.

[0027] In an embodiment, R5 is selected from isopropyl, isopropylidene, 2-butyl (sec-butyl), 2-butylidene, tertiary-butyl, 3-ethyl-3-pentyl.

[0028] In an embodiment, at least one of the dotted lines is a double bond.

[0029] In an embodiment, Ri is any of the groups from H, Et, n-Pr, z-Pr.

[0030] In an embodiment, X is selected from -CH2OH, -CHO, -CN.

[0031] In an embodiment, R3 is Me, R4 is H and R5 is ethyl or ethylidene.

[0032] In one particular embodiment, a preferred class of compounds of formula (I) can be represented by any of the following formulae (I-un-a), (I-un-b) and (I-un-c)

[0033] R4 R2 R4 R2 R4 R2

[0034]

[0035] formula (I-un-a) formula (I-un-b) formula (I-un-c) wherein X, Ri, R2, R3 and R4 are defined as above for the same radicals of main formula (I) compounds, and

[0036] wherein R6 and R7 can be independently any of the groups from H, Me, Et, preferably from H, Me.

[0037] In an embodiment, Ri, R2 and R3 can be any of the groups from H and Me.

[0038] In an embodiment, R4 can be any of the groups from H and Me. 09545(2) 4

[0039] In an embodiment, Ri, R2 and R3 can be any of the groups from H and Me, R4 can be any of the groups from H and Me, and R6 and R7 can be independently any of the groups from H and Me.

[0040] In another embodiment, compounds of formula (I) 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) 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) of this invention can be used as any one of its regioisomers or a mixture of its regioisomers.

[0041] 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).

[0042] Further, the compounds of formula (I) 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.

[0043] In an embodiment, there is provided a novel mixture of compounds of formula (I) or of compounds of formulae (I-un-a), (I-un-b) and (I-un-c) comprising at least four isomers.

[0044] For example, two isomers exhibit a different position of a double bond (called regioisomers) while two isomers exhibit a geometrical difference (either termed cis or trans or E or Z). Said example is illustrated by the Compounds 1 v / s 2, 3 v / s 4, 5 v / s 6, and 7 v / s 8 wherein compounds 1 and 2 differ in the position of a double bond; compounds 3 and 4 differ in the position of a double bond, compounds 5 and 6 differ in the position of a double bond, compounds 7 and 8 differ in the position of a double bond

[0045] In another embodiment, the mixture comprises at least four stereoisomers.

[0046] For example, there may be a double bond but no possibility of cis or trans or E or Z but there could be two or more chiral centres, thus generating at least four stereoisomers. Said example is illustrated by Compounds 11 and 14 (2-chiral centres and hence 4 stereoisomers). 09545(2) 5

[0047] For example, there may not be any double bond but there could be two or more chiral centres, thus generating at least four or even more stereoisomers. Said example is illustrated by Compounds 37 (2 chiral centres and hence 4 stereoisomers), 40 (3 chiral centres and hence 8 stereoisomers), 46 (4 chiral centres and hence 16 stereoisomers).

[0048] For example, there may be a double bond with a possibility of cis or trans or E or Zand additionally there could be two or more chiral centres, thus generating at least four stereoisomers. Said example is illustrated by Compounds 2, 4, 6, 8, 9, 10.

[0049] DETAILED DESCRIPTION

[0050] 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.

[0051] The compounds of formula (I) may be used alone, as mixtures thereof, or in combination with a base material.

[0052] 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.

[0053] The compounds of formula (I) 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. 09545(2) 6

[0054] 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) 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.

[0055] According to a particularly preferred embodiment of the invention, in addition to a compound of formula (I) 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.

[0056] The compounds of formula (I) as described herein above may be employed in a consumer product base simply by directly mixing at least one compound of formula (I), or a fragrance composition comprising said compound or compounds of formula (I) 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.

[0057] 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) 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), 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) of the present invention as hereinabove described, the odor notes of a consumer product base can be improved, enhanced, and / or modified. 09545(2) 7

[0058] This invention discloses fragrance, flavour and / or deodorizing / masking compositions comprising compounds of formula (I).

[0059] The invention discloses odorous compounds of formula (I). Particularly, the invention discloses fragrance, flavour and / or deodorizing / masking compounds of formula (I) and their method of synthesis.

[0060] Formula (I) is denoted as

[0061] R4R2

[0062] R3 Me R-|

[0063]

[0064] Formula (I)

[0065] Wherein X, Ri, R2, R3, R4 and R5 are defined as above.

[0066] In another embodiment, compounds of formula (I) 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) 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) of this invention can be used as any one of its regioisomers or a mixture of its regioisomers.

[0067] It is an advantage of the invention that the disclosed compounds exhibit geranium, melonal, lily-of-the-valley (muguet), floral, and / or aldehydic type notes. In addition, perfumery compositions comprising these compounds described herein also exhibit geranium, melonal, lily-of-the-valley (muguet), floral, and / or aldehydic type odor profiles.

[0068] An embodiment of the present invention relates to an odorous composition comprising compounds of formula (I). Particularly, the invention discloses fragrance, flavor and / or deodorizing / masking composition comprising one or more compounds of formula (I) and one or more adjuvants. 09545(2) 8

[0069] In general, in addition to the 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.

[0070] In an advantageous embodiment of the present invention, the odorous compounds of formula (I) are selected from the following compounds:

[0071] Compound Number) Name

[0072] 1) 4,6-dimethylnon-6-en-l-ol

[0073] 2) 4,6-dimethylnon-7-en-l-ol

[0074] 3) 4,6-dimethylnon-6-enal

[0075] 4) 4,6-dimethylnon-7-enal

[0076] 5) 3,4,6-trimethylnon-6-en-l-ol

[0077] 6) 3,4,6-trimethylnon-7-en-l-ol

[0078] 7) 3,4,6-trimethylnon-6-enal

[0079] 8) 3,4,6-trimethylnon-7-enal

[0080] 9) 2,4,6-trimethylnon-7-en-l-ol

[0081] 10) 2,4,6-trimethylnon-7-enal

[0082] 11) 4,6-dimethyl-7-methylenenonan-l-ol

[0083] 12) 4,6,7-trimethylnon-6-en-l-ol

[0084] 13) 4,6,7-trimethylnon-7-en-l-ol

[0085] 14) 4,6-dimethyl-7-methylenenonanal

[0086] 15) 4,6,7-trimethylnon-6-enal

[0087] 16) 4,6,7-trimethylnon-7-enal

[0088] 17) 3,4, 6-trimethyl-7 -methyl enenonan- 1 -ol

[0089] 18) 3,4,6,7-tetramethylnon-6-en-l -ol

[0090] 19) 3,4,6,7-tetramethylnon-7-en-l-ol

[0091] 20) 3,4,6-trimethyl-7-methylenenonanal

[0092] 21) 3,4,6,7-tetramethylnon-6-enal

[0093] 22) 3,4,6,7-tetramethylnon-7-enal

[0094] 23 ) 2,4, 6-trimethyl-7 -methyl enenonan- 1 -ol

[0095] 24)2,4,6,7-tetramethylnon-6-en-l-ol 09545(2) 9

[0096] 25)2,4,6,7-tetramethylnon-7-en-l-ol

[0097] 26)2,4,6-trimethyl-7-methylenenonanal

[0098] 27)2,4,6,7-tetramethylnon-6-enal

[0099] 28)2,4,6,7-tetramethylnon-7-enal

[0100] 29)4,7,8,8-tetramethylnon-6-en-l-ol

[0101] 30)4,7,8,8-tetramethylnon-6-enal

[0102] 31) 3,4,7,8,8-pentamethylnon-6-en-l-ol

[0103] 32) 3,4,7,8,8-pentamethylnon-6-enal

[0104] 33) 2,4,7, 8, 8-pentamethylnon-6-en- 1 -ol

[0105] 34)2,4,7,8,8-pentamethylnon-6-enal

[0106] 35) 4,6-dimethylnon-6-enenitrile

[0107] 36) 4,6-dimethylnon-7-enenitrile

[0108] 37) 4,6-dimethylnonanenitrile

[0109] 38) 3,4,6-trimethylnon-6-enenitrile

[0110] 39) 3,4, 6-trimethylnon-7 -enenitrile

[0111] 40) 3,4,6-trimethylnonanenitrile

[0112] 41)2,4,6-trimethylnon-6-enenitrile

[0113] 42)2,4,6-trimethylnon-7-enenitrile

[0114] 43) 3,4,6-trimethyl-7-methylenenonanenitrile

[0115] 44) 3,4,6,7-tetramethylnon-6-enenitrile

[0116] 45) 3,4,6,7-tetramethylnon-7-enenitrile

[0117] 46) 3,4,6,7-tetramethylnonanenitrile

[0118] The unsaturated compounds of said 46 compounds can advantageously be represented by any of the above (I-un-a), (I-un-b) and (I-un-c) formulae

[0119]

[0120] formula (I-un-a) formula (I-un-b) formula (I-un-c)

[0121] In an embodiment according to the present invention, the fragrance, flavor and / or deodorizing / masking composition comprises a compound of formula (I) that is selected from any of the compounds and / or from a mixture of two or more of the said compounds given 09545(2) 10

[0122] above, in particular from any one or a mixture of two or more of the said 46 compounds cited above.

[0123] 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 fragrance, flavor and / or deodorizing / masking composition(s) and / or compound(s) of formula (I) described herein may be integrated into building materials, wall and floor coverings, vehicle components, and the like.

[0124] The compounds of formula (I) 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:

[0125] Natural products such as:

[0126] 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 09545(2) 11

[0127] 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.

[0128] Synthetic raw materials for instance:

[0129] 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, 09545(2) 12

[0130] 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.

[0131] 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.

[0132] Aldehydes such as: Acetaldehyde, Adoxal, Aldehyde CIO, Aldehyde Cll iso, Aldehyde Cll moa, Aldehyde Cll undecylenic, Aldehyde Cll 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, 09545(2) 13

[0133] Salicylaldehyde, Scentenal, Syringa aldehyde, Trans-4-decenal, Trans-2-dodecenal, Trans-2-hexenal, Trans-2-nonenal, Trifernal, Vanillin, Veratraldehyde, Vernaldehyde.

[0134] 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.

[0135] 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.

[0136] Phenols such as: Butylated hydroxyanisole, Dihydroeugenol, Dimethyl hydroquinone, Dimethyl resorcinol, Eugenol pure, Guaiacol, Isoeugenol, Meta cresol, Methyl diantilis, Para cresol, Propenyl guaethol, Thymol, Ultravanil. 09545(2) 14

[0137] 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, Yara yara.

[0138] 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,

[0139] 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.

[0140] Sulphur compounds such as: Corps cassis, Dibutyl sulphide, Dimethyl sulphide, Exovert, Grapefruit thiol, Oxane, Ribes mercaptan, Sulfurol, Thiocineol.

[0141] Nitriles such as: Cinnamyl nitrile, Citronellyl nitrile, Citronitrile, Clonal, Cumin nitrile, Hexyl cyclopentanone, Irisnitrile, Lemonile, Peonile, Tridecyl nitrile, Agrumen nitrile, n-decyl nitrile.

[0142] Oximes such as: Buccoxime, Labienoxime, Stemone.

[0143] 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.

[0144] Nitro compound such as: Musk Ketone.

[0145] Schiff bases such as: Aurantiol, Helianthral, Ligantraal, Verdantiol. 09545(2) 15

[0146] 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.

[0147] The compounds of formula (I) can accordingly advantageously be used for the production of fragrance, flavor and / or deodorizing / masking compositions also comprising, 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.

[0148] 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), at least one ester and / or one alcohol (other than compound (I), 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) 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.%.

[0149] PREPARATION / SYNTHESIS

[0150] The synthesis of the compounds of this invention have been illustrated in Schemes 1 to 6. As shown in step 1 of scheme 1, allylation of a ketone II was performed with allyl chloride under basic conditions to afford an alkenone HI. Step 2 involved Fe-catalyzed reductive coupling of III with an α,β-unsaturated ester to afford ketoester IV. In an embodiment, the iron catalyst used is tris(acetylacetonato)iron(III) [abbreviated as Fe(acac)3]. In Step 3, the compound IV was reduced with sodium borohydride to afford a hydroxyester V that was subjected to an acid-catalyzed dehydration in step 4 to afford an alkenoate VI. In step 5, compound VI was reduced with lithium aluminum hydride to furnish the desired alkenols VII of Formula (I), wherein X = -CH2OH. Step 6 entailed oxidation of this alcohol with TEMPO to afford the desired alkenals VIII of Formula (I), wherein X = -CHO. 09545(2) 16

[0151] Scheme 2 depicts synthesis of substituted analogues of Formula (I). In step 1 of this scheme, addition of a Grignard reagent to the ketoester IV from Scheme 1 afforded a tertiary hydroxyester IX. Acid-catalyzed dehydration of the compound IX in step 2 gave an alkenoate X which was further reduced with lithium aluminum hydride (step 3) to furnish the desired alkenols XI of Formula (I), wherein X = -CH2OH. Step 4 entailed oxidation of this alcohol with TEMPO to furnish the desired alkenals XII of Formula (I), wherein X = -CHO.

[0152] Scheme 3 illustrates synthesis of substituted nitrile of this invention. In step 1, alkenone III underwent Fe-catalyzed reductive coupling with an α,β-unsaturated nitrile to afford a ketonitrile XIII. Step 2 involved reduction of ketone group in compound XIII with sodium borohydride to produce hydroxynitriles XIV which on subsequent acid-catalyzed dehydration (step 3) furnished an alkenenitrile XV of formula (I), wherein X = -CN.

[0153] In step 1 of Scheme 4, addition of a Grignard reagent to the ketonitrile XIII from Scheme 3 afforded a tertiary hydroxynitrile XVI. In step 2, acid-catalyzed dehydration of the compound XVI yielded an alkenenitrile XVII of Formula (I), wherein X = -CN.

[0154] Scheme 1:

[0155] Step 2

[0156] Step 3 Step 1 Fe(acac)3, TMDS

[0157] Base EtOH, ethylene glycol NaBH4ci

[0158] Step 4

[0159] Step 5

[0160]

[0161] VIII 09545(2) 17

[0162] Scheme 2:

[0163] Step 1 Step 2

[0164] Step 3 LiAIH4

[0165] Step 4 [O]

[0166]

[0167] X = -CH20H, -CH0,

[0168] -COOMe

[0169]

[0170] Formula (I) 09545(2) 18

[0171] Scheme 3:

[0172] Step 1 Step 2 Fe(acac)3, TMDS EtOH, ethylene glycol

[0173] R3 Me R-,

[0174] XIV

[0175] Step 3

[0176] Acid Catalyzed Dehydration

[0177] Scheme 4:

[0178] Step 1 Step 2 R4MgX Acid Catalyzed Dehydration

[0179] Dry THF

[0180] R3 Me R-,0°cR3Me R1

[0181] XIII XVI

[0182]

[0183] Alternatively, as shown in Scheme 5, ketoester IV was subjected to Wittig reaction to afford alkenoate XVIII which on reduction with lithium aluminum hydride produced alkenol XIX, which in turn was oxidized to alkenal XX. 09545(2) 19

[0184] Scheme 5:

[0185] Step 1 Step 2

[0186] O R? OMe R4-P+Ph3Br" R4R? OMe LiAIH4

[0187] n-BuLi, THF

[0188] R3Me R-|

[0189] XVIII

[0190] R3Me R-j X = -CH2OH, -CHO, -COOMe Formula (I)

[0191]

[0192] In a similar fashion, ketonitrile XIII from Scheme 3 was subjected to the Wittig reaction to afford alkenenitrile XXI as shown in Scheme 6.

[0193] Scheme 6:

[0194] R4-P+Ph3Br

[0195] n-BuLi, THF

[0196]

[0197]

[0198] The developed synthetic route constitutes a unique and inventive approach for preparing new compounds featuring a methyl substituent at the 4thcarbon position, i.e. including a Cs-chain extension reaction, with a potential for generating a double bond in position C6-C7 or C7-C8 after ketone reduction and dehydration.

[0199] The synthesis of the preferred class of compounds of this invention is illustrated in the following Schemes 1 A to 6 A. 09545(2) 20

[0200] Scheme 1A:

[0201] Step 2 Fe(acac)3, TMDS

[0202] VII

[0203] Step 6 [O]

[0204]

[0205] 09545(2) 21

[0206] Scheme 2A:

[0207] Step 1 Step 2

[0208] Step 3 LiAIH4

[0209] Step 4 [O]

[0210]

[0211] Scheme 3A:

[0212] Step 1steP2

[0213] Step 3 Acid Catalyzed Dehydration

[0214]

[0215] 09545(2) 22

[0216] Scheme 4A:

[0217] Step 1 Step 2

[0218] R4MgxHO R4R2Acid Catalyzed

[0219] Dehydration

[0220] ° °C R / R6R3Me R1

[0221]

[0222] XVI

[0223]

[0224] XVII

[0225] Scheme 5A:

[0226] Step 1 Step 2 R4-P+Ph3Br n-BuLi, THF

[0227] XVIII

[0228] Scheme 6A:

[0229] R4-P+Ph3Br n-BuLi, THF

[0230]

[0231] In Step (4), the acid-catalysed dehydration yields a mixture of cis / trans (EIZ) isomers with the double bond located at either the 6thor 7thposition, resulting in a mixture of at least four compounds. 09545(2) 23

[0232] EXAMPLES

[0233] Example 1:

[0234] Synthesis of a mixture of 4,6-dimethylnon-6-en-l-ol (Compound 1) and 4,6-dimethylnon-7-en-l-ol (Compound 2):

[0235] Step 1: Synthesis of 4-methylhept-6-en-3-one

[0236] 4-methylhept-6-en-3-one was prepared according to Gary A. Molander and Carlos del Pozo Losada, J. Org. Chem. 1997, 62(9), 2935-2943 with little modification as follows.

[0237] A 3 -neck 5 L round bottom flask equipped with an overhead stirrer, addition funnel was charged with pentan-3-one (1407 g, 16.3 mol, 2.5 eqv) and 1000 ml of Tetrahydrofuran. To this reaction mixture, potassium tert-butoxide (733 g, 6.5 mol, 1 eqv) was added lot wise at 0 °C and the mixture was stirred at 0 °C for 1 h. At this temperature 3 -chloroprop- 1-ene (500 g, 6534 mmol) was added dropwise with stirring for 2 h and it was monitored by GC. The reaction mixture was poured into ice-cold water and extracted with ethyl acetate (2 x 500 ml). The combined organic extracts were washed with water (1 x 500 mL) and brine (1 x 500 mL), dried (Na₂SO₄) and concentrated under reduced pressure. The crude reaction mass was purified by fractional distillation to get 4-methylhept-6-en-3-one (500 g, 3962 mmol, 60% yield) as a colorless liquid. The characterization data of the above compound matches with that reported in literature.

[0238] ¹H NMR (400 MHz, CDCl₃) δ 5.75 - 5.60 (m, 1H), 5.04 - 4.93 (m, 2H), 2.65 - 2.48 (m, 1H), 2.51 -2.36 (m, 2H), 2.39 - 2.29 (m, 1H), 2.16 - 1.99 (m, 1H), 1.11 - 0.96 (m, 6H).

[0239] IR (in cm'1): 1711, 1641

[0240] Step 2: Synthesis of methyl 4,6-dimethyl-7-oxononanoate

[0241] A 3 -neck 10 L round bottom flask equipped with an overhead stirrer, a thermometer pocket and a reflux condenser was charged with methyl acrylate (337 g, 3914 mmol), ethanol (1 L), Fe(acac)3 (126 g, 357 mmol) and TMDS (Tetramethyldisiloxane) (479 g, 3566 mmol). To this reaction mixture, 4-methylhept-6-en-3-one (500 g, 3962 mmol) was added at room temperature. Then the solution was slowly heated to 55-60 °C and was refluxed for 6 hr. The dark colored reaction mixture was then cooled to 0 °C and quenched with chilled 4N HC1 (400 ml) and the reaction mixture was extracted with ethyl acetate (2 x 300 mL). The combined organic layers were separated and washed with aqueous saturated sodium bicarbonate (300 mL) and saturated brine (200 mL). The organic layer was concentrated under reduced pressure. 09545(2) 24

[0242] The resulting material was purified by fractional distillation to give methyl 4,6-dimethyl-7-oxononanoate (356 g, 42% yield) as a colorless liquid.

[0243] ‘HNMR (400 MHz, CDCh) 83.63 (m, 3H), 2.66-2.57 (m, 1H), 2.48-2.40 (m. 2H), 2.32-2.25 (m, 2H), 1.66 - 1.61 (m, 2H), 1.48-1.40 (m, 2H), 1.39 - 1.35 (m, 1H), 1.04 - 0.99 (m, 6H), 0.86 - 0.83 (m, 3H).

[0244] IR (in cm'1): 1737, 1712

[0245] Step 3: Synthesis of methyl 7-hydroxy-4,6-dimethylnonanoate

[0246] A 3 -neck 2 L round bottom flask equipped with an overhead stirrer and a thermometer pocket was charged with methyl 4,6-dimethyl-7-oxononanoate (400 g, 1866 mmol), methanol (600 ml) and cerium (III) chloride heptahydrate (139 g, 373 mmol). To this reaction mixture was added sodium tetrahydroborate (21.18 g, 560 mmol) lot wise at 0 °C and the mixture was stirred at 25 °C for 5 h. The reaction mixture was poured into water (500 mL), and extracted with ethyl acetate (2 x 200 ml). The combined organic layers were washed with brine, dried over sodium sulphate and concentrated to get a crude residue (400 g) which was used as such for the next step.

[0247] Step 4: Synthesis of a mixture of methyl 4,6-dimethylnon-6-enoate and methyl 4,6-dimethylnon-7-enoate

[0248] A 3 -neck 2 L round bottom flask equipped with an overhead stirrer, Dean-Stark apparatus and a thermometer pocket was charged with methyl 7-hydroxy-4,6-dimethylnonanoate (240 g, 1109 mmol), methyl cyclohexane (500 ml) and amberlyst-15 (24 g, 1 wt %). The reaction mixture was stirred at 100 °C for 5 h. The reaction mixture was cooled to 25 °C and then added to cold water (500 mL) and extracted with ethyl acetate (2 x 200 ml). The combined organic layers were washed with brine, dried over sodium sulphate and concentrated to get a crude residue (220 g). The residue was purified by flash distillation a mixture of methyl 4,6-dimethylnon-6-enoate and methyl 4,6-dimethylnon-7-enoate (101 g, 46% yield) as a colourless liquid.

[0249] ¹H-NMR (400 MHz, CDCl₃) δ 5.43 - 4.79 (m, 1H), 3.72 - 3.60 (m, 3H), 2.43 - 2.12 (m, 3H), 2.06 - 1.87 (m, 2H), 1.73 - 1.57 (m, 4H), 1.55 (dd, J= 3.8, 1.3 Hz, 2H), 1.49 - 1.31 (m, 3H), 1.26 (d, J= 12.0 Hz, 1H), 0.97 - 0.78 (m, 7H).

[0250] IR (in cm'1): 1741 09545(2) 25

[0251] Step 5: Synthesis of a mixture of 4,6-dimethylnon-6-en-l-ol (Compound 1) and 4,6-dimethylnon-7-en-l-ol (Compound 2)

[0252] A 3 -neck 1 L round bottom flask equipped with an overhead stirrer and a thermometer pocket was charged with a mixture of methyl 4,6-dimethylnon-6-enoate and methyl 4,6-dimethylnon-7-enoate (67 g, 338 mmol) and ethanol (300 ml). To the reaction mixture was added sodium tetrahydroborate (38.3 g, 1014 mmol) lot wise over 15 minutes. To the reaction mixture was then added calcium chloride (37.5 g, 338 mmol) portion wise. Slight exotherm was observed and the reaction mixture was stirred at 25 °C for 4 hours. The reaction mixture was then poured into ice-cold 3N HC1 and extracted with ethyl acetate (2 x 100 ml). The combined organic layers were washed with brine, dried over sodium sulphate and concentrated to get a crude residue (60 g). The crude residue was purified by column chromatography (ethyl acetate: hexane, 3%) to get a mixture of 4,6-dimethylnon-6-en-l-ol and 4,6-dimethylnon-7-en-l-ol (42 g, 73% yield).

[0253] ¹H-NMR (400 MHz, CDCl₃) δ 5.20 - 4.80 (m, 1H), 3.63 - 3.52 (m, 2H), 2.37 - 2.24 (m, 1H), 2.22 (s, 1H), 1.96 (m, 2H), 1.78 - 1.41 (m, 5H), 1.41 - 1.26 (m, 2H), 1.25 - 1.04 (m, 1H), 0.96 - 0.73 (m, 6H).

[0254] IR (in cm'1): 3338, 1641

[0255] GCMS: 170.2, 155.1, 139.1, 127.1, 109.1, 95.1, 81.1, 69.1, 55.1, 41.1

[0256] Odor: Green, aldehydic, citrus, rose, geranium.

[0257] Example 2:

[0258] Synthesis of a mixture of 4,6-dimethylnon-6-enal (Compound 3) and 4,6-dimethylnon-7-enal (Compound 4):

[0259] A mixture of 4,6-dimethylnon-6-en-l-ol and 4,6-dimethylnon-7-en-l-ol (26g, 153 mmol Example 1) was dissolved in ethylenedi chloride (100 ml). To this solution successively tetrabutylammonium chloride hydrate (18.07 g, 30.5 mmol), potassium carbonate (1.772 g, 12.82 mmol) and an aqueous solution (120 mL) of sodium hydrogen carbonate (10.77 g, 128 mmol) and TEMPO (2.386 g, 15.27 mmol) were added. The reaction mixture was stirred at 25 °C for 10 min. Then 1 -chloropyrrolidine-2, 5-dione (26.5 g, 198 mmol) was added portion wise to the reaction mixture. The reaction mixture was stirred at 25 °C for Ih. The reaction 09545(2) 26

[0260] mixture was then poured into cold water. The organic layer was separated and washed with saturated NaHCCh solution and brine, dried over sodium sulphate and concentrated to get a crude residue. The crude residue was purified by column chromatography (1% ethyl acetate in hexane) to get a mixture of 4,6-dimethylnon-6-enal and 4,6-dimethylnon-7-enal (8.6 g, 33% yield). This was further distilled using Kugelrohr to get 4 g of desired product.

[0261] ¹H-NMR (400 MHz, CDCl₃) δ 9.73 (m, 1H), 5.41 - 4.58 (m, 1H), 2.42 (s, 1H), 2.53 - 2.23 (m, 2H), 2.03 - 1.83 (m, 2H), 1.83 - 1.55 (m, 3H), 1.55 - 1.29 (m, 4H), 1.02 - 0.77 (m, 6H).

[0262] IR (in cm'1): 1725

[0263] GCMS: 168.2, 153.1, 139.1, 124.1, 109.1, 95.1, 82.0, 69.1, 55.1, 41.1

[0264] Odor: Very strong cucumber, melon, watery.

[0265] Example 3:

[0266] Synthesis of a mixture of 3,4,6-trimethylnon-6-en-l-ol (Compound 5) and 3,4,6-trimethylnon-7-en-l-ol (Compound 6):

[0267] A mixture of compound 5 and compound 6 was prepared as per the procedures mentioned in Example 1. In step 2, methyl crotonate was used instead of methyl acrylate.

[0268] ‘HNMR (400 MHz, CDCh) 55.48 - 4.86 (m, 1H), 3.82 - 3.51 (m, 2H), 2.44 - 2.15 (m, 1H), 2.10 - 1.83 (m, 2H), 1.76 - 1.46 (m, 6H), 1.46 - 1.16 (m, 3H), 1.02 - 0.56 (m, 8H).

[0269] IR (in cm4): 3326

[0270] GCMS: 184.2, 166.1, 153.1, 140.2, 124.1, 111.1, 95.1, 82.1, 69.1, 55.1, 41.1

[0271] Odor: Floral, rose, muguet, geranium.

[0272] Example 4:

[0273] Synthesis of a mixture of 3,4,6-trimethylnon-6-enal (Compound 7) and 3,4,6-trimethylnon-7-enal (Compound 8):

[0274] This was synthesized by oxidation of the mixture of compound 5 and compound 6. 09545(2) 1

[0275] ‘HNMR (400 MHz, CDCh) 69.79 - 9.64 (m, 1H), 5.45 - 4.78 (m, 1H), 2.54 - 2.28 (m, 1H), 2.27 - 1.82 (m, 4H), 1.63 (ddd, J = 12.4, 5.4, 3.1 Hz, 1H), 1.58 - 1.49 (m, 1H), 1.38 (dtd, J = 16.6, 7.3, 2.6 Hz, 1H), 0.99 - 0.74 (m, 12H).

[0276] IR (in cm'1): 1725

[0277] GCMS: 182.2, 164.2, 149.1, 138.1, 123.1, 109.1, 95.1, 82.0, 69.1, 55.1, 41.1

[0278] Odor: Very strong aldehydic, green, floral, rosy.

[0279] Example 5:

[0280] Synthesis of a mixture of 2,4,6-trimethylnon-6-en-l-ol and 2,4,6-trimethylnon-7-en-l-ol (Compound 9)

[0281] Mixture of 2,4,6-trimethylnon-6-en-l-ol and 2,4,6-trimethylnon-7-en-l-ol (compound 9) was prepared as per the procedures mentioned in Example 1. In step 2, methyl methacylate was used instead of methyl acrylate.

[0282] ‘HNMR (400 MHz, CDCh) 85.26 - 4.75 (m, 1H), 3.59 - 3.28 (m, 2H), 2.51 - 2.37 (m, 1H), 2.07 - 1.84 (m, 3H), 1.72 - 1.50 (m, 5H), 1.48 - 1.34 (m, 1H), 1.33 - 1.20 (m, 1H), 1.14 -0.98 (m, 1H), 0.98 - 0.73 (m, 9H).

[0283] IR (in cm4): 3326

[0284] GCMS: 184.2, 166.1, 153.1, 140.2, 124.1, 111.1, 95.1, 82.1, 69.1, 55.1, 41.1

[0285] Odor: Rosy, aldehydic and green

[0286] Example 6:

[0287] Synthesis of mixture of 2,4,6-trimethylnon-6-enal and 2,4,6-trimethylnon-7-enal (Compound 10):

[0288] This was synthesized by oxidation of mixture of 2,4,6-trimethylnon-6-en-l-ol and 2,4,6-trimethylnon-7-en-l-ol (compound 9) as per the procedure mentioned in Example 2.

[0289] ‘HNMR (400 MHz, CDCh) 69.70 - 9.47 (m, 1H), 5.42 - 4.83 (m, 1H), 2.60 - 2.21 (m, 2H), 2.08 - 1.79 (m, 3H), 1.76 - 1.45 (m, 5H), 1.46 - 1.30 (m, 1H), 1.24 (m, 1H), 1.14 - 0.99 (m, 3H), 0.99 - 0.74 (m, 6H).

[0290] IR (in cm'1): 1726

[0291] GCMS: 184.2, 166.1, 153.1, 140.2, 124.1, 111.1, 95.1, 82.1, 69.1, 55.1, 41.1 09545(2) 28

[0292] Odor: Fresh aldehydic, marine, green, coriander like

[0293] Example 7:

[0294] Synthesis of mixture of (4S,6S)-4,6-dimethyl-7-methylenenonan-l-ol, (4R,6S)-4,6-dimethyl-7-methylenenonan-l-ol, (4S,6R)-4,6-dimethyl-7-methylenenonan-l-ol and (4S,6R)-4,6-dimethyl-7-methylenenonan-l-ol (Compound 11):

[0295] A 3-neck 500 mL round bottom flask equipped with an overhead stirrer and a thermometer pocket was charged with methyltriphenylphosphonium bromide (60.0 g, 168 mmol) and tetrahydrofuran (100 ml). Then 2 equivalents of 1.6 M / / -butyllithium (105 mL) were added dropwise at 0 °C. The reaction mixture was stirred for 1 h at the same temperature and methyl 4,6-dimethyl-7-oxononanoate (Step 2 product from Example 1) (18 g, 84 mmol) was then added. The reaction was continued at 25 °C for 3 hours. The reaction mixture was poured into a saturated NH₄Cl solution. The phases were separated. The aqueous phase was extracted with ethyl acetate (2x 100 mL). The combined organic layer was washed with brine, dried over sodium sulphate and concentrated to get crude residue. The crude residue was purified by column chromatography (2-3% ethyl acetate-hexane) to get a diastereomeric mixture of methyl 4,6-dimethyl-7-methylenenonanoate (5 g, 28% yield).

[0296] A diastereomeric mixture of methyl 4,6-dimethyl-7-methylenenonanoate was reduced with NaBH₄ and CaCl₂ in ethanol according to the protocol in step 5 of Example 1 to get a diastereomeric mixture of 4,6-dimethyl-7-methylenenonan-l-ol (Compound 11).

[0297] ’H NMR (400 MHz, CDCh) 5 4.81 - 4.62 (d, 2H), 3.62 (t, J = 6.6, 1.2 Hz, 2H), 2.33 - 2.16 (m, 1H), 2.05 - 1.89 (m, 2H), 1.67 - 1.55 (m, 2H), 1.47 - 1.28 (m, 3H), 1.23 (q, J = 6.8 Hz, 1H), 1.19 - 1.07 (m, 1H), 1.06 - 0.94 (m, 6H), 0.86 (d, J = 6.4 Hz, 3H).

[0298] IR (in cm-1): 3337, 1641

[0299] GCMS: 184.2, 167.1, 151.2, 127.1, 109.1, 95.1, 82.0, 69.1, 55.1, 41.1

[0300] Example 8: 09545(2) 29

[0301] Synthesis of mixture of (4S,6S)-4,6-dimethyl-7-methylenenonanal, (4R,6S)-4,6-dimethyl-7-methylenenonanal, (4S,6R)-4,6-dimethyl-7-methylenenonanal and (4R,6R)-4,6-dimethyl-7-methylenenonanal (Compound 14):

[0302] A diastereomeric mixture of 4,6-dimethyl-7-methylenenonan-l-ol (Example 7) was oxidized to a diastereomeric mixture of 4,6-dimethyl-7-methylenenonanal according to the protocol mentioned in Example 2.

[0303] ‘HNMR (400 MHz, CDCh) 89.76 - 9.66 (m, 1H), 4.97 - 4.85 (m, 1H), 2.54 - 2.28 (m, 2H), 2.28 -2.10 (m, 1H), 2.14 - 1.96 (m, 1H), 2.00 - 1.91 (m, 2H), 1.94- 1.83 (m, 1H), 1.80 - 1.52 (m, 3H), 1.47 - 1.30 (m, 2H), 1.04 - 0.86 (m, 8H), 0.90 - 0.77 (m, 5H), 0.81 - 0.70 (m, 1H).

[0304] IR (in cm-l): 1725, 1641

[0305] GCMS: 182.2, 164.2, 149.1, 135.1, 123.1, 109.1, 97.1, 84.1, 69.1, 55.1, 41.1

[0306] Odor: Very strong white floral marine aldehydic.

[0307] Example 9:

[0308] Synthesis of mixture of 4,6-dimethylnon-6-enenitrile (Compound 35) and 4,6-dimethylnon-7-enenitrile (Compound 36)

[0309] Step 1: Synthesis of 4,6-dimethyl-7-oxononanenitrile

[0310] A 3 -neck 1 L round bottom flask equipped with an overhead stirrer, a thermometer pocket and a reflux condenser was charged with acrylonitrile (20 g, 377 mmol), ethanol (100 mL), ethylene glycol (20 mL), Fe(acac)3 (13.3 g, 37.7 mmol) and TMDS (Tetramethyldisiloxane) (50.6 g, 377 mmol). To this reaction mixture, 4-methylhept-6-en-3-one (40g, 317 mmol) was added at room temperature. Then the solution was slowly heated to 60 °C and was refluxed for 6 hr. The dark colored reaction mixture was then cooled to 0 °C and quenched with chilled 4N HC1 (50 ml) and the reaction mixture was extracted with ethyl acetate (2 x 50 mL). The combined organic layers were separated and washed with aqueous saturated sodium bicarbonate (100 mL) and saturated brine (100 mL). The organic layer was concentrated under reduced pressure. The resulting material was purified by fractional distillation to give 4,6-dimethyl-7-oxononanenitrile (20 g, 30% yield) as a colorless liquid. 09545(2) 30

[0311] ‘HNMR (400 MHz, CDCh) 62.66 - 2.54 (m, 1H), 2.53 - 2.37 (m, 2 H), 2.37 - 2.15 (m, 2H), 1.78 - 1.51 (m, 2H), 1.49 - 1.36 (m, 2H), 1.29- 1.20 (m, 1H), 1.08 - 0.97 (m, 6H), 0.93 -0.81 (t, 3H),

[0312] IR (in cm’1): 2245, 1710

[0313] Step 2: Synthesis of 7-hydroxy-4,6-dimethylnonanenitrile

[0314] 4,6-dimethyl-7-oxononanenitrile (14 g, 77 mmol) was dissolved in methanol (75 ml), cooled to 0 °C; then sodium borohydride (2.92 g, 77 mmol) was added portion wise. The reaction mixture was stirred at 25 °C for 3 h and then the reaction mixture was poured into water (50 mL), and extracted with ethyl acetate (2 x 50 ml). The combined organic layers were washed with brine, dried over sodium sulphate and concentrated to get crude (12 g, 90% GC purity) which was used as such for the next step.

[0315] Step 3: Synthesis of mixture of 4,6-dimethylnon-6-enenitrile (Compound 35) and 4,6-dimethylnon-7-enenitrile (Compound 36)

[0316] A 3-neck 500 mL round bottom flask equipped with an overhead stirrer, Dean-Stark apparatus and a thermometer pocket was charged with 7-hydroxy-4,6-dimethylnonanenitrile (10 g, 54.6 mmol), methyl cyclohexane (MCH) (100 ml) and 4-methylbenzenesulfonic acid hydrate (10.38 g, 54.6 mmol). The reaction mixture was refluxed for 3 h, cooled to 25 °C, quenched with cold water (100 mL) and extracted with ethyl acetate (2 x 80 ml). The combined organic layers were washed with brine, dried over sodium sulphate and concentrated to get 9 g of crude. The crude compound was purified by column chromatography using silica gel in 2-3 % ethyl acetate in hexane to get 4.2 g of mixture of 4,6-dimethylnon-6-enenitrile and 4,6-dimethylnon-7-enenitrile. It was further distilled out using Kughlohr to get mixture of 4,6-dimethylnon-6-enenitrile and 4,6-dimethylnon-7-enenitrile (3.4 g, 20.57 mmol, 37% yield) as colorless liquid. ‘HNMR (400 MHz, CDCh) 8 5.40-5.10 (m, 0.5H), 4.79 - 4.76 (m, 0.5H), 2.56 - 2.44 (m, 1H), 2.36 - 2.22 (m, 2H), 2.02 - 1.91 (m, 2H), 1.74-1.70 (m, 1H), 1.69 - 1.56 (m, 4H), 1.51 -1.32 (m, 2H), 0.98 - 0.84 (m, 6H).

[0317] IR (in cm’1): 2247

[0318] GCMS: 165.2, 150.1, 136.1, 122.1, 108.1, 96.1, 83.1, 69.1, 55.1, 41.1

[0319] Odor: Floral, very strong green, metallic.

[0320] Example 10: 09545(2) 31

[0321] Synthesis of a mixture of 3,4,6-trimethylnon-6-enenitrile (Compound 38) and 3,4,6-trimethylnon-7-enenitrile (Compound 39)

[0322] Step 1: Synthesis of 3,4,6-trimethyl-7-oxononanenitrile

[0323] A mixture of compound 38 and compound 39 was prepared as per the protocols mentioned in Example 9. A 3 -neck 1 L round bottom flask equipped with an overhead stirrer, a thermometer pocket and a reflux condenser was charged with crotonitrile (25g, 371 mmol), ethanol (125 mL), ethylene glycol (25 mL), Fe(acac)₃ (13.1 g, 37.1 mmol) and TMDS (Tetramethyldisiloxane) (49.8 g, 371 mmol). To this reaction mixture, 4-methylhept-6-en-3-one (47g, 371 mmol) was added at room temperature. Then the solution was slowly heated to 60 °C and was refluxed for 6 hr. The dark colored reaction mixture was then cooled to 0 °C and quenched with chilled 4N HC1 (50 ml) and the reaction mixture was extracted with ethyl acetate (2 x 50 mL). The combined organic layers were separated and washed with aqueous saturated sodium bicarbonate (100 mL) and saturated brine (100 mL). The organic layer was concentrated under reduced pressure. The resulting material was purified by fractional distillation to give 3,4,6-trimethyl-7-oxononanenitrile (30 g, 40% yield) as a colorless liquid. Step 2: Synthesis of 7-hydroxy-3,4,6-trimethylnonanenitrile

[0324] 3,4,6-trimethyl-7-oxononanenitrile (15 g, 77 mmol) was converted to 7 -hydroxy-3, 4, 6-trimethylnonanenitrile by the protocol mentioned in example 9 step 2.

[0325] Step 3: Synthesis of a mixture of 3,4,6-trimethylnon-6-enenitrile (Compound 38) and 3,4,6-trimethylnon-7-enenitrile (Compound 39)

[0326] 7-hydroxy-3,4,6-trimethylnonanenitrile was dehydrated to a mixture of 3,4,6-trimethylnon-6-enenitrile and 3,4,6-trimethylnon-7-enenitrile (4.7 g, 26.2 mmol, 51% yield) as per the procedure mentioned in example 9 step 3.

[0327] ‘HNMR (400 MHz, CDCh) 85.44 - 4.71 (m, 1H), 2.50 - 2.13 (m, 3H), 2.04 - 1.90 (m, 2H), 1.85 - 1.70 (m, 1H), 1.66 - 1.55 (m, 4H), 1.45 - 1.34 (m, 1H) 1.11 - 0.75(m, 9H).

[0328] IR (in cm’1): 2245

[0329] Odour: White Floral, strong cumin, green, metallic

[0330] Example 11:

[0331] Preparation of mixture of diastereomers of 3,4,6-trimethyl-7-methylenenonanenitrile: 09545(2) 32

[0332] A 3-neck 250 mL round bottom flask equipped with an overhead stirrer and a thermometer pocket charged with methyltriphenylphosphonium bromide (36.6 g, 102 mmol), tetrahydrofuran (60 ml), / / -butyllithium (64.0 ml, 102 mmol) at -60 °C was added drop wise to the reaction mixture. It was stirred at same temperature for 1 h, then 3,4,6-trimethyl-7-oxononanenitrile (intermediate of Example 10 step 1) (10 g, 51.2 mmol) was added drop wise at the same temperature. The reaction mixture was stirred at -40 °C for additional 3h and the reaction mixture was poured into a saturated NH₄Cl solution. The aqueous phase was extracted with ethyl acetate (2x 100 mL). The combined organic layer was washed with brine, dried over sodium sulphate and concentrated to get crude. The crude was purified by column chromatography (2-3% ethyl acetate-hexane) to get a diastereomeric mixture of 3,4,6-trimethyl-7-methylenenonanenitrile (5 g, 50% yield).

[0333] ‘HNMR (400 MHz, CDCh) 84.74 - 4.68 (m, 2H), 2.34 - 2.10 (m, 3H), 2.05 - 1.91 (m, 2H), 1.90 - 1.37 (m, 1H), 1.63 - 1.52 (m, 1H), 1.48 - 1.38 (m, 1H) 1.31 - 1.19(m, 1H), 1.09 - 0.95 (m, 9H), 0.86 - 0.78(m, 3H).

[0334] IR (in cm’1): 2246

[0335] Odour: Muguet, floral, metallic

[0336] Example 12:

[0337] Synthesis of a mixture of 3,4,6,7-tetramethylnon-6-enenitrile (compound 43), 3, 4,6,7-tetramethylnon-7-enenitrile (Compound 44) and 3,4,6-trimethyl-7-methylenenonanenitrile (Compound 45)

[0338] Step 1:

[0339] Synthesis of 7-hydroxy-3,4,6,7-tetramethylnonanenitrile

[0340] A nitrogen flushed three neck round bottom flask was charged with 3,4,6-trimethyl-7-oxononanenitrile (7 g, 35.8 mmol) and tetrahydrofuran (100 ml). Then methylmagnesium chloride (46.7 ml, 140 mmol) was added at -40 °C. The reaction mixture was stirred at same temperature for Ih and then the reaction mixture was quenched with saturated NH₄Cl solution at -40 °C. The aqueous phase was extracted with ethyl acetate and the combined organic layer was washed with brine, dried with sodium sulphate and concentrated. The resulting crude was 09545(2) 33

[0341] purified by column chromatography to get methyl 7-hydroxy-3,4,6,7-tetramethylnonanenitrile (6 g, 28 mmol, 79 % yield) and used for the next step.

[0342] Step 2:

[0343] Synthesis of mixture of 3,4,6,7-tetramethylnon-6-enenitrile, 3,4,6,7-tetramethylnon-7-enenitrile and 3,4,6-trimethyl-7-methylenenonanenitrile

[0344] A 3 -neck 100 mL round bottom flask equipped with an overhead stirrer, Dean-Stark apparatus and a thermometer pocket was charged with 7-hydroxy-3,4,6,7-tetramethylnonanenitrile (5 g, 23.6 mmol), methyl cyclohexane (MCH) (50 ml) and 4-methylbenzenesulfonic acid hydrate (2.25 g, 11.8 mmol). The reaction mixture was refluxed for 3 h. The reaction mixture was cooled to 25 °C, quenched with cold water (50 mL) and extracted with ethyl acetate (2 x 50 ml). The combined organic layers were washed with brine, dried over sodium sulphate and concentrated to get crude. The crude compound was purified by column chromatography to get 3.5 g (18.1 mmol, 77 % yield) of mixture of 3,4,6,7-tetramethylnon-6-enenitrile, 3, 4,6,7-tetramethylnon-7-enenitrile and 3,4,6-trimethyl-7-methylenenonanenitrile as colorless liquid. ¹H NMR (400 MHz, CDCl₃) δ 5.23 - 4.84 (m, 0.5H), 2.54 - 2.12 (m, 2.5H), 2.04 - 1.91 (m, 1H), 1.85 - 1.69 (m, 1H), 1.63 - 1.45 (m, 4H), 1.39 - 1.23 (m, 2H), 1.09 - 0.89 (m, 9H), 0.84 - 0.74 (m, 3H).

[0345] IR (in cm’1): 2245

[0346] Odour: Very strong aldehydic, citrus, metallic, slight leathery

[0347] 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.

[0348] 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.

[0349] COMPOSITION EVALUATION EXAMPLES:

[0350] Comparison using Mixture of Compounds 1 and 2 in a Fresh Floral Green Accord: 09545(2) 34

[0351] In the following example, a fresh floral green composition accord containing Linalool as the benchmarking compound was evaluated and compared against composition accord containing the mixture of compounds 1 and 2.

[0352] Composition A contains commercial compound Linalool, composition B contains a mixture of 4,6-dimethylnon-6-en-l-ol (compound 1) & 4,6-dimethylnon-7-en-l-ol (compound 2) as 10% w / w solution in IPM (Isopropyl myristate). Composition C contains only IPM and serves as blank. All above compositions were evaluated in shampoo.

[0353] Addition of mixture of compounds 1 and 2 imparts aldehydic, floral, citrus and green character to the composition and enhances natural spicy green character of accord.

[0354] Compositions A B C

[0355] Raw Materials (Parts by

[0356] Weights)

[0357] Floralozone 3.5 3.5 3.5

[0358] Hexyl Cinnamic aldehyde 22 22 22

[0359] Linalool 12 12 12

[0360] Melonal 0.5 0.5 0.5

[0361] Coumarin 0.6 0.6 0.6

[0362] Hedione 7 7 7 Dihydromyrcenol 14 14 14

[0363] Bacdenol 2 2 2

[0364] Amberonne 20 20 20

[0365] Ethyl Linalool 2 0 0

[0366] Ionone Alpha 0.4 0.4 0.4

[0367] Phenyl Ethyl Alcohol 6 6 6

[0368] Dipropylene Glycol 10 10 10

[0369] IM Alcohol 0 2 0

[0370]

[0371] 09545(2) 35

[0372] IPM 0 0 2

[0373] Total 100 100 100

[0374]

[0375] Comparison using Mixture of Compounds 3 and 4 in a Fougere Fresh Ambery Accord:

[0376] In the following example, a fresh floral green composition accord containing trans-4-decenal as the benchmarking compound was evaluated and compared against composition accord containing the mixture of compounds 3 and 4.

[0377] Composition A contains commercial compound trans-4-decenal, composition B contains a mixture of 4,6-dimethylnon-6-en-l-al (compound 3) & 4,6-dimethylnon-7-en-l-al (compound 4) as 10% w / w solution in IPM (Isopropyl myristate). Composition C contains only IPM and serves as blank. All above compositions were evaluated in shampoo.

[0378] Addition of the mixture of compounds 3 and 4 lifts the entire composition and pushes entire composition by uplifting aldehydic natural citrus top note of accord.

[0379] Compositions A B C

[0380] Raw Materials (Parts by

[0381] Weights)

[0382] Floralozone 3.15 3.15 3.15

[0383] Hexyl Cinnamic aldehyde 25 25 25

[0384] Linalool 12.5 12.5 12.5

[0385] Melonal 2 2 2

[0386] Coumarin 0.55 0.55 0.55

[0387] Hedione 8.5 8.50 8.5 Dihydromyrcenol 15 15 15

[0388] Trans 4 decanal 10% IPM 1.5 0 0.

[0389] Amberonne 14 14 14

[0390]

[0391] Calone 0.1 0.1 0.1 09545(2) 36

[0392] Forest Breeze 1 1 1 Phenyl Ethyl Alcohol 6 6 6 Dipropylene Glycol 10.7 10.7 10.7 IM Aldehyde 10% IPM 0 1.5 0 IPM 0 0 1.5 Total 100 100 100

[0393]

Claims

09545(2) 37CLAIMS1. Compound of general formula (I)R3 Me R-|Formula (I)wherein X is selected from -CH2OH, -CHO, -CN, -COOMe, -COOEt;Ri, R2 and R3 can be any of the groups from H, Me, Et, zz-Pr, z-Pr;R4 and R5 can be independently any of the groups from H, Me, Et, zz-Pr, z-Pr, zz-Bu, z- Bu, tertiary butyl, 2-butyl (sec-butyl), zz-pentyl, zz-hexyl, zz-heptyl, 3 -ethyl-3 -pentyl, zz- octyl, methylidene, ethylidene, propylidene, isopropylidene, 2-methylpropylidene, butylidene, 2-butylidene, pentylidene, hexylidene, heptylidene, octylidene with the proviso that R4 and R5 can’t be both an alkylidene in a formula (I) compound; and dotted line can be single bond or double bond.

2. Compound of general formula (I) according to claim 1 wherein R5 is selected from isopropyl, isopropylidene, 2-butyl (sec-butyl), 2-butylidene, tertiary-butyl, 3-ethyl-3- pentyl.

3. Compound of general formula (I) according to claim 1 selected from any of the following formulae (Lun-a), (I-un-b) and (Lun-c)formula (Lun-a) formula (I-un-b) formula (Lun-c) wherein X, Ri, R2, R3 and R4 are defined as in claim 1, andwherein Re and R7 can be independently any of the groups from H, Me, Et.

4. Compound of general formula (I) according to claim 3wherein Ri, R2 and R3 can be any of the groups from H and Me,wherein R4 can be any of the groups from H and Me, andwherein Re and R7 can be independently any of the groups from H and Me.09545(2) 385. Compound of general formula (I) according to claim 1 selected from a group consisting of1) 4,6-dimethylnon-6-en-l-ol2) 4,6-dimethylnon-7-en-l-ol3) 4,6-dimethylnon-6-enal4) 4,6-dimethylnon-7-enal5) 3,4,6-trimethylnon-6-en-l-ol6) 3,4,6-trimethylnon-7-en-l-ol7) 3,4,6-trimethylnon-6-enal8) 3,4,6-trimethylnon-7-enal9) 2,4,6-trimethylnon-7-en-l-ol10) 2,4,6-trimethylnon-7-enal11) 4,6-dimethyl-7-methylenenonan-l-ol12) 4,6,7-trimethylnon-6-en-l-ol13)4,6,7 -trimethylnon-7 -en- 1 -ol14)4,6-dimethyl-7-methylenenonanal15) 4,6,7-trimethylnon-6-enal16) 4,6,7-trimethylnon-7-enal17) 3,4,6-trimethyl-7-methylenenonan-l-ol18) 3,4,6,7-tetramethylnon-6-en-l-ol19) 3,4,6,7-tetramethylnon-7-en-l-ol20) 3,4,6-trimethyl-7-methylenenonanal21) 3,4,6,7-tetramethylnon-6-enal22) 3,4,6,7-tetramethylnon-7-enal23) 2,4,6-trimethyl-7-methylenenonan-l -ol24)2,4,6,7-tetramethylnon-6-en-l-ol25)2,4,6,7-tetramethylnon-7-en-l-ol26)2,4,6-trimethyl-7-methylenenonanal27)2,4,6,7-tetramethylnon-6-enal28)2,4,6,7-tetramethylnon-7-enal29)4,7,8,8-tetramethylnon-6-en-l-ol30)4,7,8,8-tetramethylnon-6-enal09545(2) 3931) 3,4,7,8,8-pentamethylnon-6-en-l-ol32) 3,4,7,8,8-pentamethylnon-6-enal33) 2,4,7, 8, 8-pentamethylnon-6-en- 1 -ol34)2,4,7,8,8-pentamethylnon-6-enal35) 4,6-dimethylnon-6-enenitrile36) 4,6-dimethylnon-7-enenitrile37) 4,6-dimethylnonanenitrile38) 3,4,6-trimethylnon-6-enenitrile39) 3,4, 6-trimethylnon-7 -enenitrile40) 3,4,6-trimethylnonanenitrile41) 2,4,6-trimethylnon-6-enenitrile, and42)2,4,6-trimethylnon-7-enenitrile43) 3,4,6-trimethyl-7-methylenenonanenitrile44) 3,4,6,7-tetramethylnon-6-enenitrile45) 3,4,6,7-tetramethylnon-7-enenitrile46) 3,4,6,7-tetramethylnonanenitrile6. Mixture of at least four isomers of compounds of general formula (I) according to any of the preceding claims.

7. Mixture according to claim 6 wherein two isomers of compounds of general formula (I) are regioisomers and exhibit a different position of a double bond.

8. Mixture according to any of claims 6 or 7 wherein four isomers of compounds of general formula (I) are stereoisomers.

9. Fragrance, flavor and / or deodorizing / masking compositions comprising a compound or a mixture according to any of claims 1 to 8 conferring lily-of-the-valley (muguet), geranium, melonal, floral, and / or aldehydic type notes.

10. Fragrance, flavor and / or deodorizing / masking composition according to claim 9 wherein the content of the compound of formula (I) is at least 0.1 wt. % or at least 1 wt. %.09545(2) 4011. Fragrance, flavor and / or deodorizing / masking composition according to any of claims 9 to 10 wherein the content of the compound of formula (I) is below 50 wt. % or below 25 wt. %.

12. Fragrance, flavor and / or deodorizing / masking composition according to any of claims 9 to 11 comprising in addition to the compound of formula (I) at least one ester and / or one alcohol, or at least a mixture of ester and alcohol, wherein the total content of the compound(s) of formula (I) together with the ester(s) and alcohol(s) is superior to 25 wt% or superior to 50 wt%.

13. Use of a fragrance, flavour and / or deodorizing / masking composition according to any of claims 9 to 12 in a perfumed or flavoured product.

14. Use of a compound or a mixture according to any of claims 1 to 8 in a perfumed or flavoured product.

15. Process for the preparation of compounds of formula (I) according to claim 1R3Me R-iX = -CH2OH, -CHO, -COOMe, -COOEtFormula (I)comprising the steps ofa. Reacting a ketone of formula (II)wherein R3 can be any of the groups from H, Me, Et, / / -Pr, z-Pr; andRs can be any of the groups from H, Me, Et, / -Pr, z-Pr, / / -Bu, z-Bu, tertiary butyl, 2- butyl (sec-butyl), / / -pentyl, / / -hexyl, / / -heptyl, 3 -ethyl-3 -pentyl, / / -octyl, methylidene, ethylidene, propylidene, isopropylidene, 2-methylpropylidene, butylidene, 2- butylidene, pentylidene, hexylidene, heptylidene, octylidene,09545(2) 41with allyl chloride or allyl bromide to get a compound of formula (III)b. Reacting the compound of formula (III) withan α,β-unsaturated esterMeO'Riwherein Ri and R2 can be any of the groups from H, Me, Et, n-Pr, i-Pr, in presence of Fe(acac)3 to get a compound of formula (IV)R2■5 TR3Me R-,IVc. Reducing the compound of formula (IV) with sodium borohydride or catalytic hydrogenation or Meerwein-Ponndorf-Verley reduction (e.g. using aluminium alkoxide catalysis) to get a compound of formula (V)OH R2OMeR5 / - Y / '^0R3Me R-|d. Subjecting the compound of formula (V) to acid-catalyzed dehydration to get a compound of formula (VI) which is the compound of formula (I) wherein A represents -COOMe09545(2) 42e. Optionally and additionally reacting the compound of formula (VI) with lithium aluminum hydride, sodium borohydride-calcium chloride (NaBH4-CaCl2) or Vitride to get a compound of formula (VII) which is the compound of formula (I) wherein A represents -CH2OHf. optionally and additionally oxidating the compound of formula (VII), for example by employing (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO) or 4-hydroxy- TEMPO along with N-chlorosuccinimide or Dess-Martin Periodinane or Swern Oxidation or Pyridinium chlorochromate (PCC), to obtain a compound of formula (VIII) which is the compound of formula (I) wherein A represents -CHO16. Process for the preparation of compounds of formula (I)R3Me R-iX = -CH2OH, -CHO, -COOMe, -COOEtFormula (I)09545(2) 43comprising the steps a and b of claim 15 followed by the steps ofc. Reacting the compound of formula (IV) with a Grignard reagent R4MgCl or R4MgBr to get a compound of formula (IX)HO R4R2 OMeR5>Y R3 Y Me RT-| ^0IXwherein R4 can be any of the groups from Me, Et, i-Pr, i-Pr, n-Bu, i-Bu, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,d. Subjecting the compound of formula (IX) to acid-catalyzed dehydration to get a compound of formula (X) which is the compound of formula (I) wherein A represents -COOMeande. Optionally and additionally reacting the compound of formula (X) with lithium aluminum hydride sodium borohydride-calcium chloride (NaBH4-CaCl2) or Vitride to get a compound of formula (XI) which is the compound of formula (I) wherein A represents -CH2OH09545(2) 44f. optionally and additionally oxidating the compound of formula (XI), for example by employing (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO) or 4-hydroxy-TEMPO along with N-chlorosuccinimide or Dess-Martin Periodinane or Swern Oxidation or Pyridinium chlorochromate (PCC), to obtain a compound of formula (XII) which is the compound of formula (I) wherein A represents -CHO17. Process for the preparation of compounds of formula (I).R3Me R-,X = -CNFormula (I)comprising the step a of claim 15 followed by the steps ofb. Reacting the compound of formula (III)with an α,β-unsaturated nitrileRiwherein R1 and R2 can be any of the groups from H, Me, Et, n-Pr, i-Pr,in presence of Fe(acac)3 to get a compound of formula (XIII)R3Me R-,XIII09545(2) 45c. Reducing the compound of formula (XIII) with sodium borohydride or catalytic hydrogenation or Meerwein-Ponndorf-Verley reduction (e.g. using aluminium alkoxide catalysis) to get a compound of formula (XIV)d. Subjecting the compound of formula (XIV) to acid-catalyzed dehydration to get a compound of formula (XV) which is the compound of formula (I) wherein A represents -CN18. Process for the preparation of compounds of formula (I).R3Me R-,X = -CNFormula (I)comprising the steps a and b of claim 17 followed by the steps ofc. Reacting the compound of formula (XIII) with a Grignard reagent R4MgCl or R4MgBr to get a compound of formula (XVI)HO R4R2„ z'k / CNR5R3Me R-iXVI09545(2) 46wherein R4 can be any of the groups from Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl;d. Subjecting the compound of formula (XVI) to acid-catalyzed dehydration to get a compound of formula (XVII) which is the compound of formula (I) wherein A represents -CNXVII19. Process for the preparation of compounds of formula (I).R3Me R-iX = -CH2OH, -CHO, -COOMe, -COOEtFormula (I)comprising the steps a and b of claim 15 to get a compound of formula (IV)c. which is reacted with a phosphonium ylide R4P+Ph3Cl' or l P+PhaBr' wherein R4 can be any of the groups from Me, Et, i-Pr, i-Pr, n-Bu, i-Bu, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,to get a compound of formula (XVIII) which is the compound of formula (I) wherein A represents -COOMeR3Me R-,XVIIId. Optionally and additionally reacting the compound of formula (XVIII) with lithium aluminum hydride sodium borohydride-calcium chloride (NaBEU-CaCh) or Vitride to09545(2) 47get a compound of formula (XIX) which is the compound of formula (I) wherein A represents -CH2OHR3Me R-iXIX; ande. optionally and additionally oxidating the compound of formula (XIX), for example by employing (2,2,6,6-Tetramethylpiperidin-l-yl)oxyl (TEMPO) or 4-hydroxy- TEMPO along with N-chlorosuccinimide or Dess-Martin Periodinane or Swern Oxidation or Pyridinium chlorochromate (PCC), to obtain a compound of formula (XX) which is the compound of formula (I) wherein A represents -CHO20. Process for the preparation of compounds of formula (I).R3Me R-,X = -CNFormula (I)comprising the steps a and b of claim 17 to get a compound of formula (XIII)c. which is reacted with a phosphonium ylide ICP+PhaCl' or FCP PF Br' wherein R4 can be any of the groups from Me, Et, i-Pr, i-Pr, n-Bu, i-Bu, tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,to get a compound of formula (XXI) which is the compound of formula (I) wherein A represents -CN09545(2) 4821. A process for preparation of a compound of formula (I) according to any of claims 15 to 20 wherein the step b) reaction is made in the presence of tris(acetylacetonato)iron(III) catalyst (also known as Fe(acac)3) and is performed in the presence of a glycol, such as ethylene glycol, and / or another solvent such as ethanol, propanol and / or THF.

22. A process for preparation of a compound of formula (I) according to claim 21 wherein step b) is performed at a temperature comprised between 50 and 65 °C.

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