Odorous compounds and method of preparation thereof

Abstract

The present invention relates to novel odorous compounds denoted by formula (A, B or C), which are useful as fragrance or flavor materials in particular in providing lily-of-the-valley (muguet) along with floral, aldehydic and / or woody 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 (A, B or C). 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 closely related formula (A, B or C) which are useful as fragrance or flavor materials, in particular, in providing lily- of-the-valley (muguet), floral, aldehydic and / or woody 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 (A, B or C). 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] Today, biosourced terpenes, derived either from wood or from plants, are known to play an important role as either fragrance ingredients for perfumes, cosmetics, detergents or flavours for seasoning. Terpenes are also predicted to be more important in the future to compete with and replace some of the current fossil-based products (Reiter et al, CHIMIA 2021, 75, 780- 787). Some fragrance industries are also pledging to use only 100% renewable and 100% biodegradable materials by 2030. (Kraft et al, Chem. Eur. J. 2024, 30, 1-36). Therefore, there is an urgent need for high impact sustainable ingredients which are produced from renewable feedstocks.

[0006] There is huge demand for muguet or lily-of-the-valley odorants. 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 the earliest examples of synthetic lily-of-the-valley odorants. Designs of Lilial® and Bourgeonal® were inspired from 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. Many fragrance companies initiated research programs for discovery of safer alternatives to Lilial®. This led to 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.

[0007] Some of the non-aromatic lily-of-the-valley odorants are Florol®, Majantol® and Mahonial®. Lily-of-the-valley odorants are often combined with other floral notes such as jasmine or with woody notes such as cedarwood or sandalwood.

[0008] Regulatory agencies are ever more stringent on 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.

[0009] Therefore, novel compounds that possess lily-of-the-valley profile along with floral, aldehydic and / or woody aspects have high demand in the perfumery market.

[0010] It is an advantage of the present invention that novel odorous compounds denoted by formula (A, B or C) are useful as fragrance or flavor materials, in particular in providing lily-of-the- valley profile, along with floral, aldehydic and / or woody type notes to perfume, aroma or deodorizing / masking compositions.

[0011] The present invention also relates to a novel process for preparation of odorous compounds of formula (A, B or C). It is an advantage of the present invention that most of the compounds of this invention can be synthesized in one step by reaction between easily available alkenes and a,P-unsaturated carbonyl compounds or an a,P-unsaturated nitriles.

[0012] INVENTION

[0013] Alpha-pinene, beta-pinene and delta-3 -carene are abundantly present in turpentine oil. Turpentine is obtained industrially by distillation of resin that is harvested from living trees, mainly pines. Industrially, alpha-pinene is isomerized under acidic conditions to afford camphene. The current invention discloses novel compounds that are synthesized from alphapinene, beta-pinene, camphene and delta-3 -carene as starting materials. The first unifying feature of this invention is that the novel compounds reported here display one or more of the following notes: lily-of-the-valley (muguet), floral, aldehydic and / or woody.

[0014] The second unifying feature of this invention is that the key chemistry step uses tris(acetylacetonato)iron(III) [abbreviated as Fe(acac)3] as a catalyst. The key reaction is Fe(acac)3-mediated reductive olefin coupling with acceptor compounds. Olefins are the alkenes described above: alpha-pinene, beta-pinene, camphene and delta-3 -carene. The acceptor compounds are typically alpha-beta unsaturated aldehydes / ketones / ester / nitriles.

[0015] The third unifying feature of this invention is that most of the times, in one or two steps, sustainable compounds can be converted into novel fragrance ingredients.

[0016] Another important characteristic of this invention is that most novel compounds are synthesized with a very high atom economy >90%. In fact, in many cases the atom economy is almost 100%.

[0017] In fact, our invention follows the following principles of Green chemistry. a) Atom Economy: very high atom economy: more than 90% b) Use of renewable feedstocks: All above starting materials are available from turpentine which is harvested from pine trees. These are not petrochemical-based raw materials. c) Reduce derivatives: No protecting groups or functionalization is performed. d) Catalyst used is iron-based that is abundantly available. No precious metal is used.

[0018] This invention discloses fragrance, flavor and / or deodorizing / masking compositions comprising particular 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.

[0019] The invention further discloses particular odorous compounds of formula (I) per se, as well as its stereoisomers or a mixture thereof and / or regioisomers or a mixture thereof.

[0020] Particularly, the invention discloses fragrance, flavor and / or deodorizing / masking particular compounds of formula (I) formula (I) wherein

[0021] X = -CHO, -COORi, -CN, or -C(=O)CH3

[0022] M = O, or -CRx or -CRxRy

[0023] Ri, R2, R3, R4, Rs, 5, R7, Rs, R9 and Rio can be

[0024] H, -CH2, Me, Et, zz-Pr, z-Pr, zz-Bu, z-Bu, allyl, vinyl (-CH=CH2), -CH=CHMe (1- propenyl), or -C(Me)=CH2(2 -propenyl) n = 0 or 1

[0025] Y= CH=C(Me)2, Me, Et, zz-Pr, z-Pr, zz-Bu, z-Bu dotted line can be single bond or no bond.

[0026] In an embodiment, Ri to Rio are selected from alkyl or alkylidene groups having up to 4 carbon atoms. For example, Ri to Rio are independently selected from a group consisting of methyl, ethyl, zz-propyl, isopropyl, zz-butyl, isobutyl, tertiary -butyl, allyl, vinyl, 1 -propenyl and 2- propenyl.

[0027] Our initial attempts focussed on synthesis of novel odorants from beta pinene and alpha pinene. In fact, under the reaction conditions of this invention, both beta pinene and alpha pinene give the same products. Hence, both beta pinene and alpha pinene can be used interchangeably. We soon relized that camphene and delta-3 -carene can also be used under the same conditions to afford novel odorants that should have odor profiles similar to the odorants derived from beta pinene / alpha pinene. This can be represented by the following compounds of general formula A, B or C that possess lily-of-the-valley (muguet), floral, aldehydic and / or woody notes.

[0028] R-i = R2= R3 = H, Alkyl or Alkenyl from C-1-C5

[0029] X = -CHO, -COOR-i , -CH2OH, -CN, or -C(=0)CH3

[0030] In an embodiment,

[0031] X = -CHO, -COORi, -CH2OH, -CN, or -C(=O)CH3

[0032] Ri, R2, R3, are selected from

[0033] H, Me, Et, zz-Pr, z-Pr, zz-Bu, z-Bu, tertiary butyl, allyl, vinyl (-CH=CH2), -CH=CHMe (1-propenyl), -C(Me)=CH2 (2-propenyl), zz-pentyl, or isopentyl.

[0034] This invention discloses fragrance, flavor and / or deodorizing / masking compositions comprising compounds of formula (A, B or C). Here the compounds of formula (A, B or C) can be any one of its stereoisomers or a mixture of one or more of these stereoisomers. Further, compounds of formula (A, B or C) can be one of its regioisomers or a mixture of one or more of its regioisomers.

[0035] The invention further discloses odorous compounds of formula (A, B or C) per se, as well as its stereoisomers or a mixture thereof and / or regioisomers or a mixture thereof.

[0036] In another embodiment, compounds 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 this invention 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 this invention can be used as any one of its regioisomers or a mixture of its regioisomers.

[0037] 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 (A, B or C). Further, the compounds 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.

[0038] DETAILED DESCRIPTION

[0039] 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.

[0040] The compounds of formula (A, B or C) may be used alone, as mixtures thereof, or in combination with a base material.

[0041] 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.

[0042] The compounds of formula (A, B or C) 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.

[0043] According to a preferred embodiment of the invention, the fragrance, flavor and / or deodorizing / masking composition contains at least one compound according to formula (A, B or C) 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.

[0044] According to a particularly preferred embodiment of the invention, in addition to a compound of formula (A, B or C) 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.

[0045] The compounds of formula (A, B or C) as described herein above may be employed in a consumer product base simply by directly mixing at least one compound of formula (A, B or C), or a fragrance composition comprising said compound or compounds of formula (A, B or C) 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 nano capsules, 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.

[0046] 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 (A, B or C) 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 (A, B or C), 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 (A, B or C) of the present invention as hereinabove described, the odor notes of a consumer product base can be improved, enhanced, and / or modified.

[0047] This invention discloses fragrance, flavour and / or deodorizing / masking compositions comprising compounds of formula (A, B or C). The invention discloses odorous compounds of formula (A, B or C). Particularly, the invention discloses fragrance, flavour and / or deodorizing / masking compounds of formula (A, B or C) and their method of synthesis.

[0048] In an embodiment, Formula (A, B or C) are denoted as

[0049] Wherein

[0050] X = -CHO, -COORi, -CH2OH, -CN, or -C(=O)CH3

[0051] Ri, R2, R3, are selected from

[0052] H, Me, Et, zz-Pr, z-Pr, zz-Bu, z-Bu, tertiary butyl, allyl, vinyl (-CH=CH2), -CH=CHMe (1-propenyl), -C(Me)=CH2 (2-propenyl), / / -pentyl, or isopentyl.

[0053] In an embodiment, Ri to R3 are selected from hydrogen; or alkyl or alkenyl groups having up to 5 carbon atoms. For example, Ri to R3 are independently selected from a group consisting of methyl, ethyl, / / -propyl, isopropyl, / / -butyl, isobutyl, tertiary butyl, allyl, vinyl, 1-propenyl and 2-propenyl, / / -pentyl, isopentyl.

[0054] In another embodiment, compounds of formula (A, B or C) 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 (A, B or C) 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 (A, B or C) of this invention can be used as any one of its regioisomers or a mixture of its regioisomers. It is an advantage of the invention that the disclosed compounds exhibit lily-of-the-valley profile along with floral, aldehydic and or woody type notes. In addition, perfumery compositions comprising these novel compounds described herein also exhibit lily-of-the- valley profile along with floral, aldehydic and or woody type odor profiles.

[0055] An embodiment of the present invention relates to an odorous composition comprising compounds of formula (A, B or C). Particularly, the invention discloses fragrance, flavor and / or deodorizing / masking composition comprising one or more compounds of formula (A, B or C) and one or more adjuvants.

[0056] 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.

[0057] In an advantageous embodiment of the present invention, the odorous compounds of formula (A, B or C) are selected from the following compounds:

[0058] Compound Number) Name

[0059] 1) 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanenitrile

[0060] 2) Methyl 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanoate

[0061] 3) 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)butanal

[0062] 4) 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propan-l-ol

[0063] 5) 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanal

[0064] 6) Methyl 2-methyl-3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanoate

[0065] 7) 2-Methyl-3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propan-l-ol

[0066] 8) 2-Methyl-3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanal

[0067] 9) 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)butanenitrile

[0068] 10) 2-((2,6,6-trimethylbicyclo[3.1. l]heptan-2-yl)methyl)butanal

[0069] 11) 3-methyl-2-((2,6,6-trimethylbicyclo[3.1. l]heptan-2-yl)methyl)butanal

[0070] 12) 2-((2,6,6-trimethylbicyclo[3.1. l]heptan-2-yl)methyl)pentanal

[0071] 13) 2-((2,6,6-trimethylbicyclo[3.1. l]heptan-2-yl)methyl)hexanal

[0072] 14) 5-methyl-2-((2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)methyl)hexanal

[0073] 15) 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propanenitrile 16) Methyl 3-(2,3,3-trimethylbicyclo[2.2. l]heptan-2-yl)propanoate

[0074] 17) 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propan-l-ol

[0075] 18) 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propanal

[0076] 19) Methyl 2-methyl-3-(2,3,3-trimethylbicyclo[2.2. l]heptan-2-yl)propanoate

[0077] 20) 2-Methyl-3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propan-l-ol

[0078] 21) 2-Methyl-3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propanal

[0079] 22) 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)butanenitrile

[0080] 23) 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)butanal

[0081] 24) 2-((2,3,3-trimethylbicyclo[2.2. l]heptan-2-yl)methyl)butanal

[0082] 25) 3-methyl-2-((2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)methyl)butanal

[0083] 26) 2-((2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)methyl)pentanal

[0084] 27) 4-methyl-2-((2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)methyl)pentanal

[0085] 28) 2-((2,3,3-trimethylbicyclo[2.2. l]heptan-2-yl)methyl)hexanal

[0086] 29) 5-methyl-2-((2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)methyl)hexanal

[0087] 30) Methyl 3-(3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)propanoate

[0088] 31) 3-(3,7,7-trimethylbicyclo[4.1.0]heptan-3-yl)propan-l-ol

[0089] 32) 3-(3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)propanal

[0090] 33) Methyl 2-methyl-3-(3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)propanoate

[0091] 34) 2-Methyl-3-(3,7,7-trimethylbicyclo[4.1.0]heptan-3-yl)propan-l-ol

[0092] 35) 2-Methyl-3-(3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)propanal

[0093] 36) 3-(3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)butanal

[0094] 37) 3-(3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)butanenitrile

[0095] 38) 2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)butanal

[0096] 39) 3-methyl-2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)butanal

[0097] 40) 2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)pentanal

[0098] 41) 2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)hexanal

[0099] 42) 5-methyl-2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)hexanal

[0100] 43) 2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)heptanal

[0101] 44) 6-methyl-2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)heptanal

[0102] In an embodiment according to the present invention, the fragrance, flavor and / or deodorizing / masking composition comprises a compound of formula (A, B or C) that is selected from any of the compounds and / or from a mixture of two or more of the said compounds amongst the 44 compounds cited above, in particular from any one or a mixture of two or more of the said 44 compounds cited above.

[0103] In an embodiment according to the present invention, the fragrance, flavor and / or deodorizing / masking composition comprises a compound of formula (A) that is selected from any of the compounds and / or from a mixture of two or more of the said compounds amongst the compounds 1) to 14) cited above, in particular from any one or a mixture of two or more of the said compounds 1) to 14) compounds cited above, for example the compounds 1) to 3).

[0104] In an embodiment according to the present invention, the fragrance, flavor and / or deodorizing / masking composition comprises a compound of formula (B) that is selected from any of the compounds and / or from a mixture of two or more of the said compounds amongst the compounds 15) to 29) cited above, in particular from any one or a mixture of two or more of the said 15) to 29) compounds cited above.

[0105] In an embodiment according to the present invention, the fragrance, flavor and / or deodorizing / masking composition comprises a compound of formula (C) that is selected from any of the compounds and / or from a mixture of two or more of the said compounds amongst the compounds 30) to 44) cited given above, in particular from any one or a mixture of two or more of the said 30) to 44) compounds cited above.

[0106] 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 (A, B or C) described herein may be integrated into building materials, wall and floor coverings, vehicle components, and the like.

[0107] The compounds of formula (A, B or C) 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:

[0108] Natural products such as:

[0109] 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.

[0110] Synthetic raw materials for instance:

[0111] 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.

[0112] 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.

[0113] 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

[0114] 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, IsoIone 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. 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

[0115] Phenols such as: Butylated hydroxyanisole, Dihydroeugenol, Dimethyl hydroquinone, Dimethyl resorcinol, Eugenol pure, Guaiacol, Isoeugenol, Meta cresol, Methyl diantilis, Para cresol, Propenyl guaethol, Thymol, Ultravanil.

[0116] 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

[0117] 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,

[0118] 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. Sulphur compounds such as: Corps cassis, Dibutyl sulphide, Dimethyl sulphide, Exovert, Grapefruit thiol, Oxane, Ribes mercaptan, Sulfurol, Thiocineol.

[0119] Nitriles such as: Cinnamyl nitrile, Citronellyl nitrile, Citronitrile, Clonal, Cumin nitrile, Hexyl cyclopentanone, Irisnitrile, Lemonile, Peonile, Tridecyl nitrile, Agrumen nitrile, n-decyl nitrile.

[0120] Oximes such as: Buccoxime, Labienoxime, Stemone.

[0121] 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.

[0122] Nitro compound such as: Musk Ketone.

[0123] Schiff bases such as: Aurantiol, Helianthral, Ligantraal, Verdantiol.

[0124] 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.

[0125] The compounds of formula (A, B or C) 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.

[0126] 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 (A, B or C), at least one ester and / or one alcohol (other than compound (A, B or C), 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 (A, B or C) 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.%. PREPARATION / SYNTHESIS

[0127] In an embodiment of the present invention, as depicted in the following illustrating scheme, an alkene P was treated with an acceptor molecule such as an a,P-unsaturated carbonyl compound Q to afford the desired compounds of the invention A or B or C. If alkene used is beta-pinene or alpha-pinene, then product A is obtained. Use of camphene leads to formation of product B whereas when delta-3 -carene is employed as the olefin, C is the product formed. ; Catalyst

[0128] I Hydride donor

[0129] I Solvent

[0130] I Temperature

[0131] R-i = R2= R3 = H, Alkyl or Alkenyl from C-1-C5

[0132] X = -CHO, -COOR-i , -CH2OH, -CN, or -C(=0)CH3

[0133] The above reductive olefin coupling is performed in the presence of Tetramethyldisiloxane (TMDS) as a reducing agent. In a preferred embodiment, this reaction takes place in the presence of tris(acetylacetonato)iron(III) catalyst abbreviated as Fe(acac)3. Said reaction can advantageously be performed in the presence of a solvent, for example, ethylene glycol, ethanol, propanol, THF.

[0134] Reaction operating conditions will be fine-tuned by the man skilled in the art; atmospheric pressure and a range of temperatures comprised between 50 and 65 °C, for example between 55 and 60°C, can advantageously be used.

[0135] Synthetic procedures and characterization data of some selected compounds is given below.

[0136] Example 1:

[0137] General procedure for the synthesis of compounds of General formula (A, B or C): Synthesis of 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanenitrile (Compound 1):

[0138] A 3-neck 500 mL round bottom flask equipped with an overhead stirrer, a thermometer pocket and a reflux condenser was charged with acrylonitrile (58.4 g, 1101 mmol), Ethanol (250 ml), ethyleneglycol (50 mL), Fe(acac)3 (12.9 g, 36.5 mmol) and TMDS (49.3 g, 367 mmol). To this reaction mixture, alpha pinene or beta pinene (50 g, 367 mmol) was added at room temperature. Then the solution was slowly heated to 55-60 °C and was refluxed for 16 hr. The dark colored reaction mixture was then cooled to 0 °C and quenched with chilled 4(N) HC1 (200 ml) and the reaction mixture was extracted with ethyl acetate (2 x 200 mL). The combined organic layers were separated and was washed with aqueous saturated sodium bicarbonate (200 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-(2,6,6- trimethylbicyclo[3.1.1]heptan-2-yl)propanenitrile (46 g, 57% yield) as a colorless liquid. Odour profile: rnuguet, floral, strong sandal, ambery IR (Neat): 2907, 2245, 1466 cm’1

[0139] ‘H-NMR (400 MHz, CDC13): 8 2.20-2.14 (m, 2 H), 1.88-1.76 (m, 4 H), 1.66-1.47 (m, 6 H), 1.22 (s, 3 H), 1.11 (s, 3 H), 1.03 (s, 3 H).

[0140] 13C-NMR (100.6 MHz, CDCI3): 6 120.6, 50.9, 40.4, 39.5, 39.2, 37.0, 29.4, 28.4, 28.2, 26.2, 25.5, 24.1, 12.3

[0141] GCMS (m / z): 190.2 (M+), 176.1, 148.1.

[0142] Example 2: Synthesis of methyl 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanoate (Compound 2):

[0143] This compound was synthesized by the general procedure mentioned above using P-pinene and methyl acrylate.

[0144] Odour profile: woody, sandal, sweet

[0145] 'H-NMR (400 MHz, CDCh): 8 3.56 (s, 3 H), 2.19-2.08 (m, 2 H), 1.76-1.62 (m, 4 H), 1.53-1.40 (m, 6 H), 1.53 (s, 3 H), 0.89 (s, 3 H), 0.74 (s, 3 H).

[0146] GCMS (m / z): 224.3 (M+)

[0147] IR (Neat): 2906, 1739, 1435 cm’1

[0148] Example 3:

[0149] Synthesis of 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)butanal (Compound 3):

[0150] A 3-neck 500 mL round bottom flask equipped with an overhead stirrer, a thermometer pocket and a reflux condenser was charged with (£)-but-2-enal (50 g, 713 mmol)) (crotonaldehyde), Ethanol (50 ml), Fe(acac)3 (12.60 g, 35.7 mmol) and TMDS (96 g, 713 mmol). To this reaction mixture, alpha pinene or beta pinene (97.1 g, 713 mmol) was added at room temperature. Then the solution was slowly heated to 55-60 °C and was refluxed for 16 hr. The dark colored reaction mixture was then cooled to 0 °C and quenched with chilled 4(N) HC1 (200 ml) and the reaction mixture was extracted with ethyl acetate (2 x 200 mL). The combined organic layers were separated and was washed with aqueous saturated sodium bicarbonate (200 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-(2,6,6- trimethylbicyclo[3.1.1]heptan-2-yl)butanal (66.8 g, 45% yield) as a colorless liquid.

[0151] Odour profile: Floral, fresh creamy, coconut, watery.

[0152] 'H-NMR (400 MHz, CDCh): 6 9.75 (m, 1H), 2.57 - 2.48 (m, 1H), 2.10 - 2.08 (m, 2H), 2.00 - 1.91 (m, 3H), 1.80 - 1.72 (m, 2H), 1.63 (s, 3H), 1.50 -1.43 (m, 1H), 1.31 - 1.19 (m, 2H), 0.87 - 0.83 (m, 3H), 0.77 (d, J= 1.3 Hz, 3H), 0.72 (dd, J= 3.6, 1.4 Hz, 3H).

[0153] GCMS (m / z): 208.2 (M+), 175.2, 135.1.

[0154] IR (Neat): 2964, 2923, 1723 cm’1

[0155] Example 4:

[0156] Synthesis of 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propan-l-ol (Compound 4): A 3-neck 500 mL round bottom flask equipped with an overhead stirrer, a thermometer pocket and a reflux condenser was charged with methyl 3-(2,6,6-trimethylbicyclo[3.1.1] heptan-2- yl)propanoate, (Example 2, 15.0 g, 66.86 mmol)) and PEG-400 (150 ml). Then sodium borohydride (7.58 g, 200.58 mmol) was added portionwise in 30 minutes at room temperature. The reaction mixture was then heated at 70 °C for 24 h and then it was cooled to room temperature. The reaction mixture was quenched with 10% aqueous HC1 solution (100 mL) and the aqueous layer was extracted with di chloromethane (2 x 100 mL). Combined organic layer was washed with water (2 x 200 mL), sodium bicarbonate solution (200 mL) followed by brine (100 mL). The organic layer was dried over sodium sulfate and the solvent was evaporated under reduced pressure. Crude material was purified by silica gel (100-200 mesh) column chromatography using gradient elution using 10-20% ethyl acetate / w-hexane as an eluent to afford desired product 3-(2,6,6-trimethylbicyclo[3.1.1] heptan-2-yl)propan-l-ol (7.47 g, 57%) as a colourless liquid.

[0157] Odour profile: Floral, mild muguet

[0158] IR (Neat): 3325.8, 2904.2, 2869.3. cm’1

[0159] 'H-NMR (400 MHz, CDCh): 6 3.64 - 3.55 (m, 2 H), 2.09 -2.07 (m, 1 H), 1.94 - 1.78 (m, 3 H), 1.66 - 1.61 (m, 2 H), 1.56 - 1.40 (m, 6 H), 1.28 - 1.18 (m, 4 H), 1.16 (s, 3 H), 0.99 (s, 3 H).

[0160] GC-MS (m / z): 196.2 (M+), 163.2, 135.1.

[0161] Example 5:

[0162] Synthesis of 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanal (Compound 5):

[0163] To a solution of 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propan-l-ol, (Example 4, 10.0 g, 50.93 mmol, 1 eq) at 25-30 °C in 1,2-dichloroethane (60 g, 10 eq) was successively added tetrabutylammonium chloride (2.8 g, 10.18 mmol, 50% aqueous solution, 0.2 eq) and TEMPO (0.40 g, 2.54 mmol, 0.05 eq). Then a solution of potassium carbonate (0.59 g, 4.28 mmol, 0.084 eq) and sodium bicarbonate (4.50 g, 42.78 mmol, 0.84 eq) in water (100 mL) was added and the reaction mixture was stirred for 10 min. ThenA-chlorosuccinimide (8.84 g, 66.2 mmol, 1.3 eq) was added portionwise 25 °C over a period of 15 min. The reaction mixture was stirred at 25 °C for 2 hrs. The aqueous layer was separated and organic layer washed with water (20 mL). The organic layer was successively washed with 10% sodium carbonate solution, water (2 x 20 mL) and brine (20 mL). The solvent was evaporated under reduced pressure and the resulting crude material was purified by silica gel (100-200 mesh) column chromatography using gradient elution using 5-10% ethyl acetate / w-hexane as an eluent to afford the desired product 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanal (5.9 g, 60 %) as a colourless liquid.

[0164] Odour profile: White floral, camphor, minty

[0165] IR (Neat): 2904.3, 17.24.1, 1465.2. cm’1

[0166] 'H-NMR (400 MHz, CDCh): 6 9.76 (s, 1H), 2.42 - 2.06 (m, 3H), 1.92 - 1.67 (m, 4H), 1.66 - 1.45 (m, 4H), 1.24 - 1.14 (m, 4H), 1.07 - 0.97 (m, 6H).

[0167] GC-MS (m / z): 194.2 (M+), 161.1, 133.1.

[0168] Example 6:

[0169] Step 1:

[0170] Synthesis of methyl 2-methyl-3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanoate:

[0171] This compound was synthesized as per the general procedure in Example 1, using beta-pinene and methyl methacrylate:

[0172] IR (Neat): 2963.03, 1738.53, 1458.0 cm’1

[0173] ‘H-NMR (400 MHz, CDCh): 8 3.63 (s, 3 H), 2.55 - 2.45 (m, 2 H), 2.11 - 1.68 (m, 6 H), 1.64 - 1.36 (m, 4 H), 1.34 - 0.88 (m, 8 H), 0.83 - 0.73 (m, 3 H).

[0174] GC-MS (m / z): 281.1, 238.2, 207.1, 173.1,143.1

[0175] Step 2:

[0176] Synthesis of 2-methyl-3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propan-l-ol (Compound 7):

[0177] This compound was synthesized from the above step 1 product by the experimental procedure of Example 4.

[0178] Odour profile: Floral, mild galbanum type

[0179] IR (Neat): 3340.0, 2915.7, 1708.0, 1465.9 cm’1

[0180] 1H NMR (400 MHz, CDCls): 6 5.35 (bs, 1H), 3.51 - 3.40 (m, 1H), 3.36 - 3.20 (m, 1H), 2.60 (s, 1H), 2.00 - 1.87 (m, 2 H), 1.87 - 1.64 (m, 4 H), 1.38 - 1.10 (m, 5 H), 1.10 - 0.92 (m, 5 H), 0.92 - 0.73 (m, 6 H).

[0181] GC-MS (m / z): 211.1, 195.1, 167.2, 149.1, 109.1, 81.1

[0182] Example 7: Synthesis of 2-methyl-3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanal (Compound 8):

[0183] This compound was synthesized from the compound in step 2 of Example 6 by the experimental procedure of Example 5.

[0184] Odour profile: Aldehydic, sweet, minty

[0185] IR (Neat): 2910.6, 2700.5, 1725.0, 1456.7 cm’1

[0186] ‘HNMR (400 MHz, CDCh): 6 9.58 - 9.43 (m, 1 H), 2.48 - 2.36 (m, 1 H), 2.18 - 1.94 (m, 2 H), 1.92 - 1.64 (m, 4 H), 1.64 - 1.34 (m, 3 H), 1.34 - 1.18 (m, 3 H), 1.18 - 1.00 (m, 6 H), 0.90 - 0.72 (m, 4 H).

[0187] GC-MS (m / z): 208.2, 190.2, 175.5, 152.1 135.1, 95.1, 81.1

[0188] Example 8:

[0189] Synthesis of 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)butanenitrile (Compound 9):

[0190] This compound was synthesized as per the general procedure in Example 1, using beta pinene and crotonitrile.

[0191] Odor profile: Strong floral, herbal

[0192] IR (Neat): 2964.4, 2925.3, 2246.5. cm’1

[0193] ‘H-NMR (400 MHz, CDCh): 8 2.53 - 2.33 (m, 1H), 2.09 - 1.82 (m, 4H), 1.80 - 1.67 (m, 2H), 1.62 (q, J = 1.3 Hz, 2H), 1.58 - 1.36 (m, 2H), 1.30 - 1.08 (m, 2H), 1.04 (d, J = 6.6 Hz, 3H), 1.02 - 0.99 (m, 1H), 0.86 - 0.70 (m, 6H).

[0194] GC-MS (m / z): 205.3 (M+).

[0195] Example 9:

[0196] Synthesis of 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propanenitrile (Compound 15):

[0197] This compound was synthesized as per the general procedure in Example 1, using camphene and acrylonitrile.

[0198] Odour profile: Woody, sandal, cedar like

[0199] IR (Neat): 2935.8 , 2245.0, 1476.2, 1446.9 cm’1 'H-NMR (400 MHz, CDCh): 6 2.22 (t, J= 8.0 Hz, 2 H), 1.86 - 1.75 (m, 3 H), 1.70 - 1.63 (m,

[0200] 2 H), 1.61 - 1.54 (m, 1 H), 1.53 - 1.46 (m, 1 H), 1.33 - 1.21 (m, 2 H), 1.06 - 1.04 (m, 1 H), 0.94 (s, 3 H), 0.87 (s, 3 H), 0.81 (s, 3 H).

[0201] 13C-NMR (100.6 MHz, CDCh): 6 120.8, 50.9, 45.7, 42.8, 42.1, 34.5, 33.9, 26.6, 23.6, 23.1, 23.0, 18.7, 13.9.

[0202] GC-MS (m / z): 191.2, 176.1, 148.1

[0203] Example 10:

[0204] Synthesis of methyl 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propanoate (Compound 16):

[0205] This compound was synthesized as per the general procedure in Example 1, using camphene and methyl acrylate:

[0206] Odour profile: Mild woody.

[0207] IR (Neat): 2937.5, 2880.9, 1738.9, 1435.9, 1473.6 cm’1

[0208] 'H-NMR (400 MHz, CDCh): 6 3.64 (s, 3 H), 2.27 - 2.16 (m, 2 H), 1.87 - 1.81 (m, 2 H), 1.76 - 1.47 (m, 5 H), 1.26 - 1.21 (m, 2 H), 1.03 - 1.01 (m, 1 H), 0.95 (s, 3 H), 0.86 (s, 3 H), 0.79 (s,

[0209] 3 H).

[0210] 13C-NMR (100.6 MHz, CDCh): 6 175.0, 51.44, 51.15, 46.14, 42.73, 42.11, 34.60, 33.11, 31.22, 26.90, 23.84, 23.31, 23.22, 19.08.

[0211] GC-MS (m / z): 221.2 (M-3H), 147.1, 119.1.

[0212] Example 11:

[0213] Synthesis of 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propan-l-ol (Compound 17):

[0214] This compound was synthesized from the compound in Example 10 by the experimental procedure of Example 4.

[0215] Odour profile: mild woody

[0216] IR (Neat): 3319.7, 2931.4, 1473.9, 1373.8 cm’1

[0217] ‘H-NMR (400 MHz, CDCh): 6 3.59 (t, J= 6.7 Hz, 2 H), 2.46 (bs, 1 H), 1.92 - 1.79 (m, 2 H), 1.64 - 1.45 (m, 5 H), 1.41 -1.20 (m, 4 H), 1.01 - 0.99 (m, 1 H), 0.94 (s, 3 H), 0.87 (s, 3 H), 0.82 (s, 3 H).

[0218] 13C-NMR (100.6 MHz, CDCh): 8 64.0, 51.2, 46.4, 42.8, 42.0, 34.6, 34.2, 29.4, 26.9, 23.9,

[0219] 23.4, 23.2, 19.4. GC-MS (m / z): 196.2,181.1,164.1,153.1,135.1.

[0220] Example 12:

[0221] Synthesis of 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propanal (Compound 18):

[0222] This compound was synthesized from the compound in Example 11 by the experimental procedure of Example 5.

[0223] Odour profile: Camphory, sandal, woody.

[0224] IR (Neat): 2932.9, 2879.8, 1723.9, 1473.5, 1390.51 cm’1

[0225] 'H-NMR (400 MHz, CDCh): 6 9.76 (s, 1H), 2.38 - 2.31 (m, 2H), 1.88 - 1.81 (m, 2 H), 1.76 - 1.49 (m, 6 H), 1.30 - 1.22 (m, 2 H), 1.05 - 1.00 (m, 1 H), 0.97 (s, 3 H), 0.88 (s, 3 H), 0.81 (s, 3 H).

[0226] 13C-NMR (100.6 MHz, CDCh): 6 203.3, 51.1, 46.3, 42.7, 42.1, 41.3, 34.5, 29.8, 26.9, 23.8,

[0227] 23.3, 19.4.

[0228] GC-MS (m / z): 194.2, 151.1, 109.1, 69.1

[0229] Example 13:

[0230] Step 1:

[0231] Synthesis of methyl 2-methyl-3-(2,3,3-ti'imethylbicyclo[2.2.1]heptan-2-yl)propanoate:

[0232] This compound was synthesized as per the general procedure in Example 1, using camphene and methyl methacrylate:

[0233] IR (Neat): 2935.5, 2880.3, 1738.1, 1459.8 cm’1

[0234] ‘H-NMR (400 MHz, CDCh): 6 3.64 (s, 3 H), 2.42 - 2.39 (m, 1 H), 2.10 - 1.50 (m, 6 H), 1.28 - 1.11 (m, 5 H), 1.08 - 0.96 (m, 5 H), 0.85- 0.73 (m, 6 H).

[0235] 13C-NMR (100.6 MHz, CDCh): 6 178.6, 51.4, 51.2, 47.02, 45.8, 43.6, 42.6, 42.1, 41.6, 37.4,

[0236] 34.4, 27.1, 23.7, 22.9, 20.4

[0237] GCMS (m / z): 238.2 (M+)

[0238] Step 2:

[0239] Synthesis of 2-methyl-3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl) propan-l-ol: This compound was synthesized from the above step 1 product by the experimental procedure of Example 4.

[0240] IR (Neat): 3334.1, 2928.2, 2875, 1472, 1375, 1030 cm’1

[0241] 'H-NMR (400 MHz, CDCh): 8 3.52 - 3.49 (m, 1 H), 3.33 - 3.26 (m, 1 H), 1.99 - 1.81 (m, 2 H), 1.65 - 1.40 (m, 5 H), 1.29 - 1.20 (m, 3 H), 1.03 - 0.86 (m, 14 H).

[0242] 13C-NMR (100.6 MHz, CDCh): 6 69.5, 51.2, 46.2, 43.8, 42.0, 41.0, 34.4, 33.5, 26.9, 23.7, 23.4, 23.2, 20.2, 19.6.

[0243] Step 3:

[0244] Synthesis of 2-methyl-3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propanal (Compound 21)

[0245] This compound was synthesized from the above step 2 product by the experimental procedure of Example 5.

[0246] Odour: Sandalwoody, Camphoraceous

[0247] GCMS (m / z): 208.3 (M+)

[0248] COMPOSITION EVALUATION EXAMPLES:

[0249] COMPOSITION EVALUATION EXAMPLE- 1 :

[0250] In the following invention, composition (A) containing the compound 3-(2,6,6- trimethylbicyclo[3.1.1]heptan-2-yl)propanenitrile (Compound 1) was compared against a composition containing commercial compound Ebanol in a woody accord fragrance for use in shampoo ( C = blank), IPM = Isopropyl myristate.

[0251] Introduction of 5.5% by weight of 10% w / w IPM solution of the compound 3-(2,6,6- trimethylbicyclo[3.1.1]heptan-2-yl)propanenitrile (Compound 1) granted a rounded woody spicy strength and bloom. Additionally, it also imparted a very nice floral character to the whole accord. On the other hand, when Ebanol as 10% weight by weight in IPM is used in the above accord, milder woody spicy character with weaker strength and bloom composition is obtained.

[0252] COMPOSITION EVALUATION EXAMPLE-2:

[0253] In the following example, a comparison was performed between compositions of 3-(2,6,6- trimethylbicyclo[3.1.1]heptan-2-yl)propanenitrile (Compound 1) and Ebanol in a fougere accord fragrance for use in shampoo ( C = blank), IPM = Isopropyl myristate.

[0254] Addition of 14.1% by weight of 10% w / w IPM solution of 3-(2,6,6- trimethylbicyclo[3.1.1]heptan-2-yl)propanenitrile (Compound 1) to the accord gives better fougere and aromatic spicy rounded character. Additionally, it also imparts increased strength to the whole accord. On the other hand, when Ebanol 10% weight by weight in IPM is used in the above accord, a much weaker Fougere profile was obtained.

Claims

CLAIMS:

1. Compound of general formula A, B or CwhereinX is selected from -CHO, -COORi, -CH2OH, -CN, and -C(=O)CH3, andRi, R2, R3, are independently selected from hydrogen and an alkyl having from one to five carbon atoms and an alkenyl having from one to five carbon atoms.

2. Compound of general formula A, B or C according to claim 1 wherein Ri, R2, R3, are selected fromH, Me, Et, zz-Pr, z-Pr, zz-Bu, z-Bu, tertiary butyl, allyl, vinyl (-COCH2), -CH=CHMe (1- propenyl), -C(Me)=CH2 (2 -propenyl), zz-pentyl, or isopentyl.

3. Compound of general formula A, B or C according to claim 1 selected from a group consisting of1) 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanenitrile2) Methyl 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanoate3) 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)butanal4) 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propan-l-ol5) 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanal6) Methyl 2-methyl-3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanoate7) 2-Methyl-3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propan-l-ol8) 2-Methyl-3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)propanal9) 3-(2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)butanenitrile10) 2-((2,6,6-trimethylbicyclo[3.

1. l]heptan-2-yl)methyl)butanal11) 3-methyl-2-((2,6,6-trimethylbicyclo[3.

1. l]heptan-2-yl)methyl)butanal12) 2-((2,6,6-trimethylbicyclo[3.

1. l]heptan-2-yl)methyl)pentanal13) 2-((2,6,6-trimethylbicyclo[3.

1. l]heptan-2-yl)methyl)hexanal14) 5-methyl-2-((2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl)methyl)hexanal15) 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propanenitrile16) Methyl 3-(2,3,3-trimethylbicyclo[2.

2. l]heptan-2-yl)propanoate17) 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propan-l-ol18) 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propanal19) Methyl 2-methyl-3-(2,3,3-trimethylbicyclo[2.

2. l]heptan-2-yl)propanoate20) 2-Methyl-3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propan-l-ol21) 2-Methyl-3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)propanal22) 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)butanenitrile23) 3-(2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)butanal24) 2-((2,3,3-trimethylbicyclo[2.

2. l]heptan-2-yl)methyl)butanal25) 3-methyl-2-((2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)methyl)butanal26) 2-((2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)methyl)pentanal27) 4-methyl-2-((2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)methyl)pentanal28) 2-((2,3,3-trimethylbicyclo[2.

2. l]heptan-2-yl)methyl)hexanal29) 5-methyl-2-((2,3,3-trimethylbicyclo[2.2.1]heptan-2-yl)methyl)hexanal30) Methyl 3-(3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)propanoate31) 3-(3,7,7-trimethylbicyclo[4.1.0]heptan-3-yl)propan-l-ol32) 3-(3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)propanal33) Methyl 2-methyl-3-(3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)propanoate34) 2-Methyl-3-(3,7,7-trimethylbicyclo[4.1.0]heptan-3-yl)propan-l-ol35) 2-Methyl-3-(3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)propanal36) 3-(3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)butanal37) 3-(3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)butanenitrile38) 2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)butanal39) 3-methyl-2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)butanal40) 2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)pentanal41) 2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)hexanal42) 5-methyl-2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)hexanal43) 2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)heptanal44) 6-methyl-2-((3,7,7-trimethylbicyclo[4.1 ,0]heptan-3-yl)methyl)heptanal4. Compound of general formula A according to any of the preceding claims.

5. Compound of general formula B according to any one of claims 1 to 3.

6. Compound of general formula C according to any one of claims 1 to 3.

7. Mixture of diastereomers of compounds of general formula A, B or C according to any of the preceding claims.

8. Mixture of diastereomers of compounds of general formula A, B or C according to claim 7 wherein the mixture is a mixture of cis and trans isomers or of E and Z isomers.

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

10. Fragrance, flavor and / or deodorizing / masking composition according to claim 9 wherein the content of the compound of formula (A, B or C) is at least 0.1 wt. %, or at least 1 wt. %.

11. Fragrance, flavor and / or deodorizing / masking composition according to any of claims 9 to10 wherein the content of the compound of formula (A, B or C) is below 50 wt. %, or below 25 wt. %.

12. Fragrance, flavor and / or deodorizing / masking composition according to any of claims 9 to11 comprising 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 (A, B or C) 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. A process for preparation of a compound of formula A, B or C by reacting an olefin P selected from beta-pinene, alpha-pinene, camphene or delta-3 -carene with an acceptor molecule according to the following scheme; CatalystI Hydride donorI Solvent■ Temperature16. A process for preparation of a compound of formula A, B or C according to claim 15 wherein the reaction takes place in the presence of a tris(acetylacetonato)iron(III) catalyst abbreviated as Fe(acac)3.

17. A process for preparation of a compound of formula (A, B or C) according to any of claims 15-16 wherein the reaction is performed in the presence of a glycol, such as ethylene glycol, and / or another solvent like ethanol, propanol and / or THF.

18. A process for preparation of a compound of formula (A, B or C) according to any of claims 15-16-17 at a temperature comprised between 50 and 65 °C, or between 55 and 60°C.

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