Odor compounds and methods for their preparation

Abstract

The present invention relates to novel odor compounds represented by formula (A, B or C) which are useful as fragrant or flavor materials, in particular for providing a lily of the valley (muguet) as well as a floral, aldehydic and / or woody note to a perfume, fragrance or deodorizing / masking composition. The present invention also relates to a fragrance, flavor and / or deodorizing / masking composition comprising the odor compounds represented by formula (A, B or C). The present invention also relates to the use of said odorants in a fragrance, flavor and / or deodorizing / masking composition according to the invention. The present invention also relates to a process for the production of said odorants / compounds.

Description

Invention Field

[0001] This invention relates to novel odor compounds represented by closely related formulas (A, B, or C), which can be used as aromatic or flavoring materials, particularly for providing lily of the valley (lily of the valley), floral, aldehyde, and / or woody scents for perfumes, aromatic, or deodorizing / masking compositions. The invention also relates to aromatic, flavoring, and / or deodorizing / masking compositions comprising odor compounds represented by formulas (A, B, or C). The invention further relates to the use of said odorants in the aromatic, flavoring, and / or deodorizing / masking compositions of the invention. The invention also relates to methods for producing said odorants / compounds and corresponding aromatic, flavoring, and / or deodorizing / masking compositions containing said odorants / compounds. Background of the Invention Currently, terpenes derived from wood or plants are known to play an important role as fragrance ingredients in perfumes, cosmetics, detergents, or as flavoring agents in condiments. They are also predicted to become even more important in the future in order to compete with and replace some current fossil-based products (Reiter et al., CHIMIA 2021, 75, 780-787). Some fragrance industries have also committed to using 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 produced from renewable raw materials.

[0003] There is a huge demand for lily of the valley or lily of the valley scent agents. It is estimated that lily of the valley scent agents account for 20% of the total fragrance ingredient market. The lily of the valley scent comprises green floral notes, typically with a fresh and sweet character. Cyclamen Aldehyde® is one of the earliest examples of synthetic lily of the valley scent agents. Lilial® and Bourgeonal® are inspired by Cyclamen Aldehyde®. Lilial® has been widely used in all categories since 1946, such as fine fragrances, shampoos, detergents, toiletries, and household cleaners. However, after studies showed reproductive toxicity in male rats, lilial® was classified as CMR 2 and ultimately banned from use in cosmetic products from March 2022. Detailed experimental studies indicated that p-tert-butylbenzoic acid (a metabolite of lilial®) was responsible for the toxic effects in rats. Many fragrance companies have initiated research projects to find safer alternatives to lilial®. This led to the discovery of numerous aromatic and non-aromatic lily of the valley scent agents. Notable examples of such aromatic lily of the valley scent agents are Florhydral®, Mimosal®, and Nympheal®. In Nympheal®, the strategically placed methyl group adjacent to the 3-carbon chain is said to be responsible for eliminating toxicity in rats.

[0004] Some non-aromatic lily of the valley scents are Florol®, Majantol®, and Mahonial®. Lily of the valley scents are often combined with other floral notes such as jasmine or with woody notes such as cedarwood or sandalwood.

[0005] Regulatory bodies are imposing increasingly stringent requirements on the introduction of novel fragrance agents for use in cosmetics. The growing restrictions on the supply of natural fragrance ingredients have revolutionized the field of synthetic fragrance ingredients. Today, there is a growing demand for novel fragrance agents / compounds and / or novel aromatic, flavorful, and / or deodorizing / masking compositions containing said fragrance agents / compounds.

[0006] Therefore, novel compounds with characteristics of lily of the valley, as well as floral, aldehyde, and / or woody notes, are in high demand in the fragrance market.

[0007] One advantage of the present invention is that the novel odor compounds represented by formula (A, B or C) can be used as aromatic or flavoring materials, particularly for providing lily of the valley characteristics, as well as floral, aldehyde and / or woody notes, to perfumes, fragrances or deodorizing / masking compositions.

[0008] This invention also relates to novel methods for preparing odor compounds of formula (A, B, or C). An advantage of this invention is that most of the compounds can be synthesized in a single step via a reaction between readily available olefins and α,β-unsaturated carbonyl compounds or α,β-unsaturated nitrile compounds.

[0009] invention α-Pinene, β-pinene, and δ-3-carene are abundant in turpentine oil. Turpentine oil is industrially obtained by distillation of resin harvested from living trees (primarily pine). Industrially, α-pinene is isomerizes under acidic conditions to provide camphene. This invention discloses novel compounds synthesized from α-pinene, β-pinene, camphene, and δ-3-carene as raw materials. A first unifying feature of this invention is that the novel compounds reported herein exhibit one or more of the following fragrance notes: lily of the valley (lily of the valley), floral, aldehyde, and / or woody.

[0010] A second unifying feature of this invention is the use of tri(acetylacetone)ferric(III) [abbreviated as Fe(acac)3] as a catalyst in the key chemical steps. The crucial reaction is the Fe(acac)3-mediated coupling with a reducing olefin of the acceptor compound. The olefin is one of the aforementioned olefins: α-pinene, β-pinene, camphene, and δ-3-carene. The acceptor compound is typically an α-β-unsaturated aldehyde / ketone / ester / nitrile.

[0011] The third unifying feature of this invention is that, most of the time, sustainable compounds can be converted into novel flavoring ingredients in one or two steps.

[0012] Another important feature of this invention is that most of the novel compounds are synthesized with very high atom economy >90%. In fact, in many cases, the atom economy is almost 100%.

[0013] In fact, this invention follows the following green chemistry principles.

[0014] a) Atom economy: Very high atom economy: greater than 90% b) Use of renewable raw materials: All of the above raw materials can be obtained from turpentine harvested from pine trees. These are not petrochemical-based raw materials.

[0015] c) Reduced derivatives: No protecting groups or functionalization were performed.

[0016] d) The catalyst used is an abundant and readily available iron-based catalyst. No precious metals are used.

[0017] This invention discloses aromatic, flavoring, and / or deodorizing / masking compositions comprising a specific compound of formula (I). Here, the compound of formula (I) can be any one of its stereoisomers or a mixture of one or more of these stereoisomers. Furthermore, the compound of formula (I) can be one of its regioisomers or a mixture of one or more of its regioisomers.

[0018] The present invention further discloses the odor compound of a specific formula (I) itself, as well as its stereoisomers or mixtures thereof and / or regioisomers or mixtures thereof.

[0019] In particular, the present invention discloses specific compounds of formula (I) with aromatic, flavorful, and / or deodorizing / masking properties. Formula (I) in X = -CHO, -COOR1, -CN, or -C(=O)CH3 M = O or –CR8 or -CR8R9 R1, R2, R3, R4, R5, R6, R7, R8, R9 and R 10 It can be H, -CH2, Me, Et, n -Pr、 i -Pr、 n -Bu、 i -Bu, allyl, vinyl (-CH=CH2), -CH=CHMe (1-propenyl) or -C(Me)=CH2 (2-propenyl) n = 0 or 1 Y = CH = C(Me)2, Me, Et, n -Pr、 i -Pr、 n -Bu、 i -Bu Dashed lines can be single keys or no keys.

[0020] In one implementation, R1 to R 10 Selected from alkyl or alkylene groups having at most four carbon atoms. For example, R1 to R2. 10 It is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, allyl, vinyl, 1-propenyl and 2-propenyl.

[0021] Our initial attempts focused on synthesizing novel odorants from β-pinene and α-pinene. In fact, under the reaction conditions of this invention, both β-pinene and α-pinene yield the same product. Therefore, β-pinene and α-pinene can be used interchangeably. We quickly realized that camphene and δ-3-carene can also be used under the same conditions to provide novel odorants that should have odor characteristics similar to those derived from β-pinene / α-pinene. This can be represented by compounds of the following general formulas A, B, or C, possessing lily-of-the-valley (lily of the valley), floral, aldehyde, and / or woody notes.

[0022] In one implementation scheme X = -CHO, -COOR1, -CH2OH, -CN, or -C(=O)CH3 R1, R2, and R3 are selected from H, Me, Et, n -Pr、 i -Pr、 n -Bu、 i -Bu, tert-butyl, allyl, vinyl (-CH=CH2), -CH=CHMe (1-propenyl), -C(Me)=CH2 (2-propenyl), n-pentyl or isopentyl.

[0023] This invention discloses aromatic, flavoring, and / or deodorizing / masking compositions comprising compounds of formula (A, B, or C). Here, the compound of formula (A, B, or C) can be any one of its stereoisomers or a mixture of one or more of these stereoisomers. Furthermore, the compound of formula (A, B, or C) can be one of its regioisomers or a mixture of one or more of its regioisomers.

[0024] The present invention further discloses the odor compound of formula (A, B or C) itself, as well as its stereoisomers or mixtures thereof and / or regioisomers or mixtures thereof.

[0025] In another embodiment, the compounds of the present invention can be chiral, for example, they can be as pure enantiomers or diastereomers or as a mixture of stereoisomers (enantiomers or diastereomers), more specifically as a mixture of enantiomers or diastereomers; for example, as R isomers S The compounds can be used as isomers, racemic mixtures, and / or non-racemic mixtures. Furthermore, the compounds of the present invention can also be advantageously used as... RR isomers SS isomers RS isomers SRThe compounds can be used as isomers, racemic mixtures, and / or non-racemic mixtures. Furthermore, the compounds of the present invention can be used as any one of their regioisomers or mixtures of their regioisomers.

[0026] By stating "any one of its regioisomers or a mixture of its regioisomers", those skilled in the art will understand that the existence of regioisomers is due to different double bond positions in the structure of formula (A, B or C).

[0027] Furthermore, the compounds of the present invention can be used as pure compounds or as mixtures of geometric isomers (diastereomers); for example, they can be Cis and trans Mixtures of isomers or as E and Z Isomers.

[0028] Detailed Explanation The term "odorant" used to characterize compounds according to the invention refers to substances that evoke a preferred pleasant odor sensation in humans; therefore, it is conventionally used to flavor industrial and hygiene products, detergents, cleaning agents, personal hygiene products, cosmetics, etc. For the purposes of this invention and the appended claims, the term "odorant" includes "aromatic substances." Aromatic substances are a term commonly used to refer to substances that provide odor and / or flavor to food.

[0029] Compounds of formula (A, B, or C) can be used alone, as a mixture thereof, or in combination with a matrix material.

[0030] As used herein, “matrix material” includes all known aroma / flavor materials selected from a wide range of natural products such as essential oils, extracts, resins or isolates, and currently available synthetic materials such as hydrocarbons, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, nitriles, oximes or heterocycles, and / or mixed with one or more ingredients or excipients / adjuvants conventionally used in aroma and / or flavor compositions in combination with odorants, such as solvents / diluents, stabilizers, carrier materials and other auxiliaries commonly used in the art.

[0031] Compounds of formula (A, B, or C) can be used in a wide range of aroma applications, such as in any area of ​​premium and functional fragrances, including perfumes, air care products, household products, laundry products, body care products, and cosmetics. The compound can be used in very varying amounts, depending on the specific application and the nature and amount of other odor components.

[0032] According to a preferred embodiment of the invention, the aromatic, flavoring, and / or deodorizing / masking composition contains at least one compound as described above according to formula (A, B, or C) in an amount of 0.00001 to 99.9 wt.%, for example 0.0001 to 95 wt.%, for example 0.001 to 25 wt.%, preferably 0.01 to 15 wt.%, more advantageously 0.1 to 10 wt.%, particularly 1 to 5 wt.%, in each case relative to the whole composition.

[0033] According to a particularly preferred embodiment of the invention, in addition to the compounds of formula (A, B or C) according to the invention, the aromatic, flavoring and / or deodorizing / masking compositions according to the invention also contain additional odorants, for example, in an amount of 0.1 to 99.9 wt.%, preferably 5-90 wt.%, particularly 15-70 wt.%, relative to the whole aromatic and / or flavoring composition.

[0034] Compounds of formula (A, B, or C) as described above can be used in a consumer product matrix simply by directly mixing at least one compound of formula (A, B, or C) or an aromatic composition containing one or more compounds of formula (A, B, or C) with the consumer product matrix; or they can be encapsulated in an earlier step with encapsulating materials such as polymers, capsules, microcapsules and / or nanocapsules, liposomes, film-forming agents, absorbents such as activated carbon or zeolite, cyclic oligosaccharides, cyclic glycoures, and mixtures of two or more thereof, or they can be chemically bonded to a substrate suitable for releasing aromatic molecules upon application of external stimuli such as light, enzymes, air, water, etc., and then mixed with the consumer product matrix.

[0035] Therefore, the present invention can be used in existing methods for manufacturing aromatic, flavorful, and / or deodorizing / masking compositions, including the introduction of one or more compounds of formula (A, B, or C) as aromatic, flavorful, and / or deodorizing / masking ingredients, which is achieved by directly incorporating said compound into a consumer product matrix or by mixing an aromatic, flavorful, and / or deodorizing / masking composition containing one or more compounds of formula (A, B, or C), and then mixing it with the consumer product matrix using conventional techniques and methods. By adding an olfactorily acceptable amount of at least one compound of formula (A, B, or C) of the present invention as described above, the odor profile of the consumer product matrix can be improved, enhanced, and / or altered.

[0036] This invention discloses aromatic, flavoring, and / or deodorizing / masking compositions comprising compounds of formula (A, B, or C).

[0037] This invention discloses odor compounds of formula (A, B, or C). In particular, this invention discloses aromatic, flavoring, and / or deodorizing / masking compounds of formula (A, B, or C) and methods for synthesizing them.

[0038] In one implementation, formula (A, B, or C) is represented as in X = -CHO, -COOR1, -CH2OH, -CN, or -C(=O)CH3 R1, R2, and R3 are selected from H, Me, Et, n -Pr、 i -Pr、 n -Bu、 i -Bu, tert-butyl, allyl, vinyl (-CH=CH2), -CH=CHMe (1-propenyl), -C(Me)=CH2 (2-propenyl), n-pentyl or isopentyl.

[0039] In one embodiment, R1 to R3 are selected from hydrogen; or alkyl or alkenyl groups having up to 5 carbon atoms. For example, R1 to R3 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, allyl, vinyl, 1-propenyl and 2-propenyl, n-pentyl, and isopentyl.

[0040] In another embodiment, the compounds of formula (A, B, or C) of the present invention can be chiral, for example, they can be as pure enantiomers or diastereomers or as mixtures of stereoisomers (enantiomers or diastereomers), more specifically as mixtures of enantiomers or diastereomers; for example, as R isomers S Isomers, racemic mixtures, and / or non-racemic mixtures may be used. Furthermore, compounds of formula (A, B, or C) may also be advantageously used as... RR isomers SS isomers RS isomers SR Isomers, racemic mixtures, and / or non-racemic mixtures may be used. Furthermore, compounds of formula (A, B, or C) of the present invention may be used as any one of their regioisomers or mixtures of their regioisomers.

[0041] One advantage of this invention is that the disclosed compounds exhibit characteristics of lily of the valley, as well as floral, aldehyde, and / or woody aroma notes. Furthermore, fragrance compositions comprising these novel compounds described herein also exhibit characteristics of lily of the valley, as well as floral, aldehyde, and / or woody aroma features.

[0042] One embodiment of the present invention relates to odor compositions comprising compounds of formula (A, B, or C). In particular, the present invention discloses aromatic, flavoring, and / or deodorizing / masking compositions comprising one or more compounds of formula (A, B, or C) and one or more adjuvants.

[0043] Typically, in addition to the novel odorants and / or aromatic, flavoring and / or deodorizing / masking compositions described herein, suitable aromatic, flavoring or deodorizing compositions may also advantageously contain conventional adjuvants, such as solvents, carriers, stabilizers, emulsifiers, humectants, dispersants, diluents, thickeners, thinners, other odorants and / or other adjuvants, etc.

[0044] In an advantageous embodiment of the invention, the odor compound of formula (A, B, or C) is selected from the following compounds: (Compound number) Name 1) 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionitrile 2) Methyl 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionate 3) 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)butyraldehyde 4) 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)prop-1-ol 5) 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionaldehyde 6) Methyl 2-methyl-3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionate 7) 2-Methyl-3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)prop-1-ol 8) 2-Methyl-3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propanal 9) 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)butyronitrile 10) 2-((2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)methyl)butanal 11) 3-Methyl-2-((2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)methyl)butanal 12) 2-((2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)methyl)pentanal 13) 2-((2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)methyl)hexanal 14) 5-Methyl-2-((2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)methyl)hexanal 15) 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propionitrile 16) Methyl 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propionate 17) 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)prop-1-ol 18) 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propionaldehyde 19) Methyl 2-methyl-3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propionate 20) 2-Methyl-3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)prop-1-ol 21) 2-Methyl-3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propanal 22) 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)butyronitrile 23) 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)butanal 24) 2-((2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)methyl)butanal 25) 3-Methyl-2-((2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)methyl)butanal 26) 2-((2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)methyl)pentanal 27) 4-Methyl-2-((2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)methyl)pentanal 28) 2-((2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)methyl)hexanal 29) 5-Methyl-2-((2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)methyl)hexanal 30) Methyl 3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)propionate 31) 3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)prop-1-ol 32) 3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)propionaldehyde 33) Methyl 2-methyl-3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)propionate 34) 2-Methyl-3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)prop-1-ol 35) 2-Methyl-3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)propanal 36) 3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)butanal 37) 3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)butyronitrile 38)2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)butanal 39) 3-Methyl-2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)butanal 40) 2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)pentanal 41) 2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)hexanal 42) 5-Methyl-2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)hexanal 43) 2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)heptanal 44) 6-Methyl-2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)heptan In one embodiment of the invention, the aroma, flavor, and / or deodorizing / masking composition comprises a compound of formula (A, B, or C) selected from any of the 44 compounds cited above and / or a mixture of two or more of the compounds cited above, particularly any one or a mixture of two or more of the 44 compounds cited above.

[0045] In one embodiment of the invention, the aromatic, flavoring, and / or deodorizing / masking composition comprises a compound of formula (A), selected from any compound 1) to 14) cited above and / or a mixture of two or more of said compounds, particularly selected from any one or a mixture of two or more of said compounds 1) to 14) cited above, such as compounds 1) to 3).

[0046] In one embodiment of the invention, the aroma, flavor and / or deodorizing / masking composition comprises a compound of formula (B) selected from any of the compounds 15) to 29) cited above and / or a mixture of two or more of the compounds, particularly any one or a mixture of two or more of the compounds 15) to 29) cited above.

[0047] In one embodiment of the invention, the aroma, flavor and / or deodorizing / masking composition comprises a compound of formula (C) selected from any compound of the above-cited compounds 30) to 44) and / or a mixture of two or more of said compounds, particularly selected from any one or a mixture of two or more of said compounds 30) to 44) mentioned above.

[0048] In one embodiment of the invention, the claimed aromatic, flavoring, and / or deodorizing / masking compositions are advantageously used as fragrance compositions. Fragrance compositions according to the invention generally comprise perfumes, colognes, eau dutoilettes, and / or eau de parfums. In one embodiment of the invention, the claimed aromatic, flavoring, and / or deodorizing / masking compositions are advantageously used in cosmetic formulations, personal care products, cleaning products, fabric softeners, and / or air fresheners, etc. Furthermore, within the scope of embodiments of the invention, the novel aromatic, flavoring, and / or deodorizing / masking compositions described herein and / or one or more novel compounds of formula (A, B, or C) can be integrated into building materials, wall and floor coverings, vehicle components, etc.

[0049] Compounds of formula (A, B, or C) can be combined with many known natural or synthetic aromatic, flavoring, and / or deodorizing / masking materials. Thus, the range of natural ingredients can include not only volatile components but also semi-volatile and slightly volatile components, and the range of synthetic ingredients can include representatives from many categories of substances, such as those described in Steffen Arctander, Perfume and Flavor Chemicals, Volumes 1 & 2, Montclair, NJ, 1969; Steffen Arctander, Perfume and Flavor Materials of Natural Origin, Elizabeth, NJ, 1960; or Horst Surburg, Johannes Panten, Common Fragrance and Flavor Materials, Wiley-VCH, Weinheim, 2016, and is apparent from the following non-limiting compilation: Natural products, such as: Parsley oil, sage oil, wormwood oil, artemisia oil, basil oil, beeswax absolute, bergamot oil, birch tar, black pepper oil, black pepper resin, camphor oil, canadensis oil, caraway oil, cardamom oil, carrot seed oil, castor oil, cedarwood leaf oil, cedarwood oil, celery seed oil, chamomile oil, cinnamon bark oil, cinnamon leaf oil, rockrose absolute, rockrose oil, citronella oil, citronellol terpenes, sage oil, refined clove oil, coriander oil (white), coriander. Coriander seed oil, cumin seed oil, cypress oil, artemisia oil, dill seed oil, elm oil, elm extract, eucalyptus oil, pine needle oil, galangal oil, geranium oil, ginger oil, grapefruit oil, guaiac oil, coriander balsam, jasmine absolute, spikenard oil, juniper berry oil, juniper leaf oil, kachur oil, razorbene absolute, razorbene extract, lavender oil, lemon oil, lemon oil terpenes, lemongrass oil, lime oil, litsea cubeba oil, litsea cubeba terpenes 、 Lobhanchoya extract, orange oil, peppermint oil, lemon peppermint oil, acacia essential oil, myrrh extract, cyperus oil, nutmeg oil, oakmoss essential oil, oakmoss extract, frankincense oil, frankincense extract, orange oil, oregano oil, palmarosa oil, patchouli oil, peppermint oil, Peruvian balsam extract, orange leaf oil, pine needle oil, pink pepper oil, rose essential oil, rose oil, rosemary oil, sandalwood oil, seaweed essential oil, spearmint oil, Sugandh kokila oil, Sugandh mantri oil, marigold oil, turmeric balsam extract, tuberose essential oil, turmeric oil, valerian oil, vetiver oil, vetiver terpenes.

[0050] Synthetic raw materials, for example: Esters, such as: hexadecaldehyde, allyl isopentoxyacetate, allyl hexanoate, allyl cyclohexylpropionate, allyl heptaate, allyl phenoxyacetate, isoamyl acetate, amyl benzoate, amyl butyrate, amyl hexanoate, amyl cinnamate, amyl isovalerate, amyl phenylacetate, amyl propionate, isoamyl salicylate, acetylacetonate oil, anisyl acetate, benzyl acetate, benzyl benzoate, benzyl butyrate, benzyl cinnamate, benzyl formate, benzyl isobutyrate, benzyl isoeugenol, benzyl propionate, benzyl salicylate, etc. Benzyl acetate, butyl acetate, butyl butyrate, butyl butyryl lactate, caryophyllene acetate, cypressene acetate, cinnamyl acetate, cinnamyl butyrate, cis-3-hexenyl acetate, cis-3-hexenyl benzoate, cis-3-hexenyl hexanoate, cis-3-hexenyl formate, cis-3-hexenyl isobutyrate, cis-3-hexenyl 2-methyl butyrate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, cis-3-hexenyl picolinate, citronellol acetate, citronellol butyrate, formic acid Citronellol, citronellol isobutyrate, citronellol propionate, citronellol terbinate, Cyclabute, cyclohexyl ethyl acetate, decyl acetate, dibutyl phthalate, diethyl malonate, diethyl phthalate, dihydromyrcene acetate, dimethyl octyl acetate, dimethyl phenylethyl acetate, dioctyl adipate, dioctyl phthalate, dimethyl benzyl acetate, dimethyl benzyl butyrate, ethyl linaloate, ethyl 2-methylbutyrate, ethyl 3-phenylpropionate Ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethyl decanoate, ethyl hexanoate, ethyl octanoate, ethyl cinnamate, ethyl heptamate, ethyl hexyl acetate, ethyl isobutyrate, ethyl laurate, ethyl nonanoate, ethyl phenoxyacetate, ethyl phenylacetate, ethyl phenylepoxypropionate, ethyl propionate, ethyl saffronate, ethyl salicylate, ethyl valerate, eugenol acetate, synthetic oakmoss (Evernyl), fumarate acetate, Floramat, frescolatateML), Fructone, Fruitate, Geraniol acetate, Geraniol butyrate, Geraniol formate, Geraniol propionate, Geraniol terbinate, Givescone, Guaiacyl acetate, Hedionate, Hedione dihydrojasmonic acid methyl ester, Helvetolide, Herbanate, Hexyl acetate, Hexyl benzoate, Hexyl butyrate, Hexyl hexanoate, Hexyl isobutyrate Ester, Hexyl propionate, Hexyl salicylate, Isobornyl acetate, Isobutyl acetate, Isobutyl phenylacetate, Isobutyl salicylate, Isoeugenol acetate, Isononyl acetate, Isopentyrate, Isopropyl 2-methylbutyrate, Isopropyl myristate, Jasmonic acid, Chlorophyll, Linaloyl acetate, Mahagonate, Manzanate, p-Menthyl acetate, Menthyl acetate, Methyl benzoate, 2-Methylbutyl acetate, Methylchamomile camomille), methyl cinnamate, methyl cyclofolate, methyl heptynecarboxylate, methyl laurate, methyl octynecarboxylate, methyl phenylacetate, methyl salicylate, methyl-2-butyrate, methyl 2-nonanoate (Neofolione), nobyl acetate, octene acetate, octyl acetate, octyl isobutyrate, p-cresol acetate, p-cresol isobutyrate, p-cresol phenylacetate, p-cresol p-phenylacetate, p-rhizoester, Peranat, phenoxyethyl isobutyrate, phenylethyl acetate, phenylethyl butyrate, phenylethyl formate, phenylethyl isobutyrate, phenylethyl phenylacetate, phenylethyl propionate. Phenylacetyl salicylate, phenethyl ethyl benzoate, phenethyl isobutyrate, isoprene acetate, Romandolide, Sagecete, styrax acetate, styrax propionate, Tangerinol, terpineol acetate, Thesaron, trans-2-hexenyl acetate, Tropicate, verdox acetate, tricyclodecenyl acetate, tricyclodecenyl propionate, vertenex acetate, vetikol acetate, vetiverylacetate, Yasmolys.

[0051] Lactones, such as: asterolactone, macrocyclic musk (Arova N), Celeriax, butyldecylolactone, propyldecylolactone, butyldodecylolactone, propyldodecylolactone, glycol brassinate, exaltolide, propylheptylolactone, butylcaprolactone, propylcaprolactone, methyl lactone, methyloctylolactone, butylnonylolactone, propylnonylolactone, octahydrocoumarin, butyloctylolactone, propyloctylolactone, Rootylone, Silvanone supra, butyl undecylolactone, propyl undecylolactone, propylpentylolactone, 10-oxahexadecanolactone (OHD musk), coumarin, cyclopentadecanolactone (Habanolide), jasmine lactone.

[0052] Aldehydes, such as: acetaldehyde, adoloxal, decanal, isoundecaldehyde, methyl octyl acetaldehyde (Aldehyde C11 moa), C11 undecenal, C11 undecenal, C12 lauraldehyde, methyl nonanal (Aldehyde C12 MNA), anisaldehyde, pentyl cinnamaldehyde, benzaldehyde, bourgeonal, borneol, cantonal, cetonal, cinnamaldehyde, cis-4-decenal, cis-6-nonenal, citral, citronellol, citronelloloxyacetaldehyde, cocal, cuminaldehyde, curgix, cyclal C), Cyclomyral, Cyclovertal, 9-Decenoal, Dupical, Empetal, Ethylvanillin, Sea Breeze Aldehyde, Anthocyanin, Geraniol, Helional®, Heptanal, Hexanal, Hexylcinnamaldehyde, Historynal® Neo, Hydratropaldehyde, Hydroxycitronellal, Intreleven aldehyde), isobutavanol, isocyclic citral, isovaleraldehyde, lily aldehyde, neocitral, macaronal, mefranal, melonal, methyl cinnamaldehyde, trans-2-cis-6-nonadienal, nonanal, octanal, oncidal, p-methylbenzaldehyde, phenylacetaldehyde, phenylpropanal, methyl citric acid B, saffron aldehyde, salicylaldehyde, scentenal, eugenol, trans-4-decenal, trans-2-dodecenal, trans-2-hexenal, trans-2-nonenal, trifernal, vanillin, veratral, vernaldehyde.

[0053] Ketones, such as: Acetanisol, acetoin, acetophenone, Aldron, allyl ionone, benzophenone, benzylacetone, calone, camphor, carvone d-, carvone l-, cashmereone, methyl cedryne, methyl ceresinate, methyl jasmone, Claritone, Cosmone, crystallide, cyclotene, damascenone, damasmone α, damasmone β, damasmone δ, damasmone γ, diacetyl, dihydroβ-ionone, dihydroisojasmone ester. isojasmonate, dimethyloctenone, Dynascone, ethylpentyl ketone, ethyl maltol, frankincense, filbertone, geranylacetone, globanone, heptacyclopentanone, ionone α, ionone β, pure ionone, Iriswood, irisone α, ambroxanone (Iso E Super), isofrankincense, isojasmone T, Isolone K, isomenthone, isophorone, cis-jasmone, Kambernoir, Kephalis, Koavone, Lavendinal, maltol, menthone, methyl acetophenone, methyl pentyl ketone, methyl heptenone, methyl hexyl ketone, methyl ionone γ, methyl naphthyl ketone β, methyl nonyl ketone, muscone, muscone, Nectaryl, Orinox, OTBC ketone, p-tert-butylcyclohexanone, Patchwood, Phantolid, Pharaone, Piperone, Plicatone, raspberry ketone, raspberry ketone methyl ether, Safraleine, Spirogalbanone pure, Tonalid, Trimofix O, Veloutone, Vetikon.

[0054] Alcohols, such as: carbonyl synthetic alcohol C13, Amber core, Ambermax, Ambrinol, pentylvinylmethanol, anisyl alcohol, santalinol, benzyl alcohol, butanol, cedrol crystals. Crystals), cinnamyl alcohol, citronellol, coumarin, decanol, dimethylbenzylmethanol, dimethyloctanol, dimethylphenylethylmethanol, dimethylheptanol, fentanyl alcohol, hexanol, isoborneol, isoborneol cyclohexanol, Javanol, Keflorol, Kohinool, lauryl alcohol, Lilyflore, linalool oxide, Mayol, menthol, Norlimbanol, octanol, Osyrol, p-tert-butylcyclohexanol, phenoxanol, phenoxyethanol, phenylethanol, phenylpropanol, propylene glycol, rosaphen, rose diol, styraxol, tricyclodecanediethanol, tetrahydrolinalool, tetrahydromyrceneol, Timberol, undecavertol, cis-3-hexenol, citronellol laevo), Cyclofloranol, dihydrolinalool, dihydromyrcetol, Dimyrcetol, Ebanol, Geraniol, Isopleurol, Linalool, Nerolidol, Nerolidol, trans-2-cis-6-nonadienol, Polysantol, Rosalva, Sandalmysore core, Sandalore, Terpinene-4-ol, Terpineol, trans-2-hexenol.

[0055] Phenolic compounds, such as: butylated hydroxyanisole, dihydroeugenol, dimethyl hydroquinone, dimethyl resorcinol, eugenol (pure), guaiacol, isoeugenol, m-cresol, Methyl diantilis, p-cresol, propenyl ethyl guaiacol, thymol, Ultravanil.

[0056] Ethers, such as: ambergris ether, anisole, carvone, benzyl isopentyl ether, benzyl isopropyl ether, benzyl isovalerate, iris ether, cedramber methyl ether, cetalox, methyl decyl ether, dibenzyl ether, dihydrorose ether, biphenyl ether, doremox, estragalole, ethyl linalool, eucalyptol, Galaxolide, Gyrane, Herbavert, lime oxide, Madrox, methyl isoeugenol, β-naphthyl isobutyl ether, nerol oxide, Nerolin bromelia, p-cresol butyl ether, p-cresol methyl ether, Petiole, phenyl ethyl methyl ether, rhubafuran, rose ether, Rosyrane, Trisamber, Vetylbois K, Yara yara.

[0057] Acetals, such as: acetal CD, acetal R, amberketal, boisambrene forte, citrathal, 1,1-diethoxyethane, Emeraldine, Freshopal, Herboxane, Indoflor, Jacinthaflor, Magnolan, Spirambrene, Viridine, Elinotaal, Glycolierral, Karanal, and Methyl pamplemousse.

[0058] Hydrocarbons, such as: bisabolene, camphene, carene δ3, caryophyllene, cedrene, p-cymene, dipentene, diphenylmethane, isolongifene, limonene d-, longifene, myrcene, naphthalene, ocimene, pinene α, pinene β, styrene, terpinene γ, terpinene oleene, 1,3,5-undecanetriene, and isopropyl gluconate (Verdoracine).

[0059] Sulfur compounds, such as: Corps cassis, dibutyl sulfide, dimethyl sulfide, Exovert, grapefruit thiol, Oxane, Ribes mercaptan, Sulfurol, Thiocineol.

[0060] Nitriles, such as: cinnamonitrile, citronitrile, clonal, cuminnitrile, hexylcyclopentanone, nonenonitrile, citronitrile, peony nitrile, tridecylnitrile, Agrumen nitrile, and n-decylnitrile.

[0061] Oximes, such as: Buccoxime, Labienoxime, and limonene.

[0062] Nitrogen-containing heterocycles, such as: 2-acetylpyrazine, 2-acetylpyridine, sec-butylquinoline, phenylpropylpyridine (Corpsracine), 2-ethyl-3,5 (or 6)-dimethylpyrazine, furfurylpyrrole, indole, isobutylquinoline, 2-isobutyl-3 (or 6)-methoxypyrazine, isopropylquinoline, Maritima, p-methylquinoline, skatole, 2,3,5-trimethylpyrazine.

[0063] Nitro compounds, such as muscone.

[0064] Schiff bases, such as: nerol, helianthral, ​​ligantraal, and verdantiol.

[0065] Other materials include: acetanilide, cyclic amine (Gardamide), fruit amide (Paradisamide), dimethyl anthranilate, methyl anthranilate, butyric acid, decanoic acid, hexanoic acid, octanoic acid, phenylacetic acid, caryophyllene oxide, cedroxyde, and Tobacarol.

[0066] Therefore, compounds of formula (A, B, or C) can be advantageously used to produce aromatic, flavoring, and / or deodorizing / masking compositions that also comprise a wide range of known odorants / aromatic, flavoring, and / or deodorizing / masking materials as apparent from the foregoing compilation. In the production of such compositions, the aforementioned known aromatic, flavoring, and / or deodorizing / masking materials can be used according to methods known to perfumers, for example, according to WA Poucher, Perfumes, Cosmetics and Soaps 2, 7th edition, Chapman and Hall, London 1974.

[0067] In one embodiment of the invention, the claimed aroma, flavor, and / or deodorizing / masking composition comprises at least one ester and / or one alcohol (different from compound (A, B, or C), if present), other than a compound of formula (A, B, or C), preferably a mixture of at least the ester and the alcohol; said ester and / or alcohol is preferably selected from the list defined above. In one embodiment of the invention, the claimed odorant composition is characterized in that the total content of the compound of formula (A, B, or C) together with said ester and / or alcohol is greater than 25 wt.%, preferably greater than 50 wt.%, for example greater than 75 wt.%, or even greater than 90 wt.%.

[0068] Preparation / Synthesis In one embodiment of the invention, as depicted in the following diagram, olefin P is treated with an acceptor molecule, such as an α,β-unsaturated carbonyl compound Q, to obtain the desired compound A, B, or C of the invention. If the olefin used is β-pinene or α-pinene, product A is obtained. The use of camphene results in the formation of product B, while when δ-3-carene is used as the olefin, C is the product formed.

[0069] The above-mentioned olefin coupling is carried out in the presence of tetramethyldisiloxane (TMDS) as a reducing agent. In a preferred embodiment, this reaction occurs in the presence of a tri(acetylacetone)ferric(III) catalyst abbreviated as Fe(acac)3.

[0070] The reaction can be advantageously carried out in the presence of a solvent, such as ethylene glycol, ethanol, propanol, or THF.

[0071] The reaction operating conditions will be fine-tuned by those skilled in the art; atmospheric pressure and a temperature range including 50 to 65°C, for example 55 to 60°C, can be advantageously used.

[0072] The following are the synthetic procedures and characterization data for some of the selected compounds.

[0073] Example: Example 1: General procedure for synthesizing compounds of general formula (A, B, or C): Synthesis of 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionitrile (compound 1): Acrylonitrile (58.4 g, 1101 mmol), ethanol (250 mL), ethylene glycol (50 mL), Fe(acac)3 (12.9 g, 36.5 mmol), and TMDS (49.3 g, 367 mmol) were charged into a 500 mL round-bottom flask equipped with a top stirrer, thermometer socket, and reflux condenser. α-pinene or β-pinene (50 g, 367 mmol) was added to this reaction mixture at room temperature. The solution was then slowly heated to 55–60 °C and refluxed for 16 hours. The dark reaction mixture was then cooled to 0 °C and quenched with cooled 4(N) HCl (200 mL), and the reaction mixture was extracted with ethyl acetate (2 x 200 mL). The combined organic layers were separated and washed with saturated aqueous sodium bicarbonate solution (200 mL) and saturated brine (100 mL). The organic layers were concentrated under reduced pressure. The material was purified by fractional distillation to obtain 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionitrile (46 g, 57% yield) as a colorless liquid.

[0074] Scent characteristics: lily of the valley, floral, strong sandalwood, amber IR (pure): 2907, 2245, 1466 cm⁻¹ -1 1 H-NMR (400 MHz, CDCl3): δ 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).

[0075] 13 C-NMR (100.6 MHz, CDCl3): δ 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 GCMS (m / z): 190.2 (M + ), 176.1, 148.1.

[0076] Example 2: Synthesis of methyl 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionate (compound 2): This compound was synthesized using β-pinene and methyl acrylate via the general procedure mentioned above.

[0077] Scent characteristics: woody, sandalwood, sweet 1 H-NMR (400 MHz, CDCl3): δ 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, 3H).

[0078] GCMS (m / z): 224.3 (M + ) IR (pure): 2906, 1739, 1435 cm⁻¹ -1 Example 3: Synthesis of 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)butyraldehyde (compound 3): Fill a 500 mL round-bottom flask with a top stirrer, thermometer socket, and reflux condenser with ( E 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)butanal (50 g, 713 mmol) (crotonaldehyde), ethanol (50 ml), Fe(acac)3 (12.60 g, 35.7 mmol) and TMDS (96 g, 713 mmol) were added to the reaction mixture at room temperature. The solution was then slowly heated to 55–60 °C and refluxed for 16 hours. The dark reaction mixture was then cooled to 0 °C and quenched with cooled 4(N) HCl (200 ml), and the reaction mixture was extracted with ethyl acetate (2 x 200 mL). The combined organic layers were separated and washed with saturated aqueous sodium bicarbonate solution (200 mL) and saturated brine (100 mL). The organic layers were concentrated under reduced pressure. The resulting material was purified by fractional distillation to give 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)butanal (66.8 g, 45% yield) as a colorless liquid. Scent characteristics: floral, fresh cream, coconut, aquatic notes 1H-NMR (400 MHz, CDCl3): δ 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).

[0079] GCMS (m / z): 208.2 (M+), 175.2, 135.1.

[0080] IR (pure): 2964, 2923, 1723 cm⁻¹ -1 Example 4: Synthesis of 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)prop-1-ol (compound 4): Methyl 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionate (Example 2, 15.0 g, 66.86 mmol) and PEG-400 (150 mL) were added to a 500 mL round-bottom flask with a top stirrer, thermometer socket, and reflux condenser. Sodium borohydride (7.58 g, 200.58 mmol) was then added in portions over 30 minutes at room temperature. The reaction mixture was then heated at 70 °C for 24 h and cooled to room temperature. The reaction mixture was quenched with 10% HCl aqueous solution (100 mL), and the aqueous layer was extracted with dichloromethane (2 x 100 mL). The combined organic layers were washed with water (2 x 200 mL), sodium bicarbonate solution (200 mL), and then brine (100 mL). The organic layers were dried over sodium sulfate, and the solvent was evaporated under reduced pressure. The crude material was purified by gradient elution using silica gel (100-200 mesh) column chromatography with 10-20% ethyl acetate / n-hexane as eluent to obtain the desired product 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)prop-1-ol (7.47 g, 57%) as a colorless liquid.

[0081] Scent characteristics: Floral, mild lily of the valley scent IR (pure): 3325.8, 2904.2, 2869.3 cm⁻¹ -1 1 H-NMR (400 MHz, CDCl3): δ 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, 4H), 1.16 (s, 3H), 0.99 (s, 3H).

[0082] GC-MS (m / z): 196.2 (M+), 163.2, 135.1.

[0083] Example 5: Synthesis of 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionaldehyde (compound 5): 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) were successively added to a solution of 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)prop-1-ol (Example 4, 10.0 g, 50.93 mmol, 1 eq) in 1,2-dichloroethane (60 g, 10 eq) at 25-30 °C. 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. Then, in portions, the mixture was added at 25 °C over 15 min. N 3-Chlorosuccinimide (8.84 g, 66.2 mmol, 1.3 eq). The reaction mixture was stirred at 25 °C for 2 h. The aqueous layer was separated, and the organic layer was washed with water (20 mL). The organic layer was washed successively with 10% sodium carbonate solution, water (2 x 20 mL), and brine (20 mL). The solvent was evaporated under reduced pressure, and the crude material was purified by gradient elution using silica gel (100-200 mesh) column chromatography with 5-10% ethyl acetate / n-hexane as eluent to give the desired product 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionaldehyde (5.9 g, 60%) as a colorless liquid.

[0084] Scent characteristics: white floral, camphor, and mint notes IR (pure): 2904.3, 17.24.1, 1465.2 cm⁻¹ -1 1 H-NMR (400 MHz, CDCl3): δ 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).

[0085] GC-MS (m / z): 194.2 (M+), 161.1, 133.1.

[0086] Example 6: Step 1: Synthesis of methyl 2-methyl-3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionate: This compound was synthesized using β-pinene and methyl methacrylate according to the general procedure in Example 1: IR (pure): 2963.03, 1738.53, 1458.0 cm⁻¹ -1 1 H-NMR (400 MHz, CDCl3): δ 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, 3H).

[0087] GC-MS (m / z): 281.1, 238.2, 207.1, 173.1,143.1 Step 2: Synthesis of 2-methyl-3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)prop-1-ol (compound 7): This compound was synthesized from the product of step 1 above using the experimental procedure of Example 4.

[0088] Scent characteristics: Floral, mild galbanum type IR (pure): 3340.0, 2915.7, 1708.0, 1465.9 cm⁻¹ -1 1H NMR (400 MHz, CDCl S):δ 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).

[0089] GC-MS (m / z): 211.1, 195.1, 167.2, 149.1, 109.1, 81.1 Example 7: Synthesis of 2-methyl-3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propanal (compound 8): This compound was synthesized from the compound in step 2 of Example 6 using the experimental procedure of Example 5.

[0090] Odor characteristics: Aldehyde, sweetness, and mint. IR (pure): 2910.6, 2700.5, 1725.0, 1456.7 cm⁻¹ -1 1 H NMR (400 MHz, CDCl3): δ 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).

[0091] GC-MS (m / z): 208.2, 190.2, 175.5, 152.1 135.1, 95.1, 81.1 Example 8: Synthesis of 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)butyronitrile (compound 9): This compound was synthesized using β-pinene and crotonitrile according to the general procedure in Example 1.

[0092] Scent characteristics: Strong floral and herbal scents IR (pure): 2964.4, 2925.3, 2246.5 cm⁻¹-1 1 H-NMR (400 MHz, CDCl3): δ 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).

[0093] GC-MS (m / z): 205.3 (M+).

[0094] Example 9: Synthesis of 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propionitrile (compound 15): This compound was synthesized using camphene and acrylonitrile according to the general procedure in Example 1.

[0095] Scent characteristics: woody, sandalwood, cedar-like IR (pure): 2935.8, 2245.0, 1476.2, 1446.9 cm⁻¹ -1 1 H-NMR (400 MHz, CDCl3): δ 2.22 (t, J = 8.0 Hz, 2 H), 1.86 – 1.75 (m, 3H), 1.70 – 1.63 (m, 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).

[0096] 13 C-NMR (100.6 MHz, CDCl3): δ 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.

[0097] GC-MS (m / z): 191.2, 176.1, 148.1 Example 10: Synthesis of methyl 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propionate (compound 16): This compound was synthesized using camphene and methyl acrylate according to the general procedure in Example 1: Scent characteristics: mild woody IR (pure): 2937.5, 2880.9, 1738.9, 1435.9, 1473.6 cm⁻¹ -1 1 H-NMR (400 MHz, CDCl3): δ 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, 1H), 0.95 (s, 3H), 0.86 (s, 3H), 0.79 (s, 3H).

[0098] 13 C-NMR (100.6 MHz, CDCl3): δ 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.

[0099] GC-MS (m / z): 221.2 (M-3H), 147.1, 119.1.

[0100] Example 11: Synthesis of 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)prop-1-ol (compound 17): This compound was synthesized from the compound in Example 10 using the experimental procedure of Example 4: Scent characteristics: mild woody IR (pure): 3319.7, 2931.4, 1473.9, 1373.8 cm⁻¹ -1 1 H-NMR (400 MHz, CDCl3): δ 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).

[0101] 13 C-NMR (100.6 MHz, CDCl3): δ 64.0, 51.2, 46.4, 42.8, 42.0, 34.6,34.2, 29.4, 26.9, 23.9, 23.4, 23.2, 19.4.

[0102] GC-MS (m / z): 196.2,181.1,164.1,153.1,135.1.

[0103] Example 12: Synthesis of 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propionaldehyde (compound 18): This compound was synthesized from the compound in Example 11 using the experimental procedure of Example 5: Odor characteristics: camphor, sandalwood, woody IR (pure): 2932.9, 2879.8, 1723.9, 1473.5, 1390.51 cm⁻¹ -1 1 H-NMR (400 MHz, CDCl3): δ 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, 1H), 0.97 (s, 3H), 0.88 (s, 3H), 0.81 (s, 3H).

[0104] 13 C-NMR (100.6 MHz, CDCl3): δ 203.3, 51.1, 46.3, 42.7, 42.1, 41.3,34.5, 29.8, 26.9, 23.8, 23.3, 19.4.

[0105] GC-MS (m / z): 194.2, 151.1, 109.1, 69.1 Example 13: Step 1: Synthesis of methyl 2-methyl-3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propionate: This compound was synthesized using camphene and methyl methacrylate according to the general procedure in Example 1: IR (pure): 2935.5, 2880.3, 1738.1, 1459.8 cm⁻¹ -1 1 H-NMR (400 MHz, CDCl3): δ 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, 6H).

[0106] 13 C-NMR (100.6 MHz, CDCl3): δ 178.6, 51.4, 51.2, 47.02, 45.8, 43.6,42.6, 42.1, 41.6, 37.4, 34.4, 27.1, 23.7, 22.9, 20.4 GCMS (m / z): 238.2 (M+) Step 2: Synthesis of 2-methyl-3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)prop-1-ol: This compound was synthesized from the product of step 1 above using the experimental procedure of Example 4.

[0107] IR (pure): 3334.1, 2928.2, 2875, 1472, 1375, 1030 cm⁻¹ -1 1 H-NMR (400 MHz, CDCl3): δ 3.52 – 3.49 (m, 1 H), 3.33 – 3.26 (m, 1H), 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, 14H).

[0108] 13 C-NMR (100.6 MHz, CDCl3): δ 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.

[0109] Step 3: Synthesis of 2-methyl-3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propanal (compound 21) This compound was synthesized from the product of step 2 above using the experimental procedure of Example 5.

[0110] Odor: Sandalwood, camphor-like GCMS (m / z): 208.3 (M+) Composition Evaluation Examples: Composition Evaluation Example-1: In the following invention, a composition (A) containing compound 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionitrile (compound 1) in a woody accord fragrance for use in shampoo is compared with a composition containing the commercial compound ebony alcohol (C = blank), IPM = isopropyl myristate. Raw materials (parts by weight) Kambernoir SHK 10 10 10 Bacdanol 8 8 8 Methyl cypressone 8 8 8 Eugenol acetate 0.5 0.5 0.5 Iso E Super 40 40 40 Isoborneol acetate 10 10 10 Isoborneol (IBCH) 8 8 8 p-tert-butylcyclohexyl acetate (PTBCA) 10 10 10 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionitrile, as a 10% w / w solution in IPM (compound 1). 5.5 0 0 Ebony alcohol, as 10% w / w in IPM 0 5.5 0 IPM 0 0 5.5 total 100 100 100 .

[0111] The introduction of a 10% w / w IPM solution of 5.5 wt% of compound 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionitrile (compound 1) provides a rounded woody spiciness intensity and bloom. Additionally, it imparts a very good floral character to the overall fragrance. On the other hand, the use of ebony alcohol (as 10 wt% in IPM) in the aforementioned fragrance results in a milder woody spiciness character with a weaker intensity and bloom.

[0112] Composition Evaluation Example-2: In the following examples, a comparison was made between a composition of 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionitrile (compound 1) and ebony alcohol in the fragrance notes for use in shampoos (C = blank), IPM = isopropyl myristate. Raw materials (parts by weight) Kambernoir SHK 7 7 7 Ambroxan 0.1 0.1 0.1 benzyl acetate 5.5 5.5 5.5 Coumarin 7.5 7.5 7.5 dihydromyrcenol 11.5 11.5 11.5 Emeraldine 1 1 1 Synthetic oakmoss (Evernyl) 0.3 0.3 0.3 Geraniol 19 19 19 Kflorol 15 15 15 Lavandin oil 7 7 7 Patchouli oil 4 4 4 Tonalid (a type of musk) 8 8 8 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionitrile, as a 10% w / w solution in IPM (compound 1). 14.1 0 0 Ebony alcohol, as 10% w / w in IPM 0 14.1 0 IPM 0 0 14.1 total 100 100 100 .

[0113] Adding a 10% w / w IPM solution of 14.1 wt% of 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionitrile (compound 1) to the fragrance resulted in a better richness and a more rounded, aromatic spicy character. It also imparted an increased intensity to the overall fragrance. On the other hand, the use of ebony alcohol (10 wt% in IPM) in the aforementioned fragrance resulted in a much weaker richness.

Claims

1. Compounds of general formula A, B or C in X is selected from -CHO, -COOR1, -CH2OH, -CN, and -C(=O)CH3, and R1, R2, and R3 are independently selected from hydrogen and alkyl and alkenyl groups having 1 to 5 carbon atoms.

2. The compound of general formula A, B or C according to claim 1 R1, R2, and R3 are selected from H, Me, Et, n -Pr、 i -Pr、 n -Bu、 i -Bu, tert-butyl, allyl, vinyl (-CH=CH2), -CH=CHMe (1-propenyl), -C(Me)=CH2 (2-propenyl), n-pentenyl or isopentenyl.

3. The compound of general formula A, B or C according to claim 1, wherein the compound is selected from... 1) 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionitrile 2) Methyl 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionate 3) 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)butyraldehyde 4) 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)prop-1-ol 5) 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionaldehyde 6) Methyl 2-methyl-3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propionate 7) 2-Methyl-3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)prop-1-ol 8) 2-Methyl-3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)propanal 9) 3-(2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)butyronitrile 10) 2-((2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)methyl)butanal 11) 3-Methyl-2-((2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)methyl)butanal 12) 2-((2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)methyl)pentanal 13) 2-((2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)methyl)hexanal 14) 5-Methyl-2-((2,6,6-trimethylbicyclo[3.1.1]hept-2-yl)methyl)hexanal 15) 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propionitrile 16) Methyl 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propionate 17) 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)prop-1-ol 18) 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propionaldehyde 19) Methyl 2-methyl-3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propionate 20) 2-Methyl-3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)prop-1-ol 21) 2-Methyl-3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)propanal 22) 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)butyronitrile 23) 3-(2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)butanal 24) 2-((2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)methyl)butanal 25) 3-Methyl-2-((2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)methyl)butanal 26) 2-((2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)methyl)pentanal 27) 4-Methyl-2-((2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)methyl)pentanal 28) 2-((2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)methyl)hexanal 29) 5-Methyl-2-((2,3,3-trimethylbicyclo[2.2.1]hept-2-yl)methyl)hexanal 30) Methyl 3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)propionate 31) 3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)prop-1-ol 32) 3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)propionaldehyde 33) Methyl 2-methyl-3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)propionate 34) 2-Methyl-3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)prop-1-ol 35) 2-Methyl-3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)propanal 36) 3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)butanal 37) 3-(3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)butyronitrile 38)2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)butanal 39) 3-Methyl-2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)butanal 40) 2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)pentanal 41) 2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)hexanal 42) 5-Methyl-2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)hexanal 43) 2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)heptanal 44) 6-Methyl-2-((3,7,7-trimethylbicyclo[4.1.0]hept-3-yl)methyl)heptanal.

4. A compound of general formula A according to any one of the preceding claims.

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

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

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

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

9. An aromatic, flavoring, and / or deodorizing / masking composition comprising a compound or mixture according to any one of the preceding claims to impart a lily of the valley (lily of the valley), floral, aldehyde, and / or woody fragrance.

10. The aroma, 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. The aromatic, flavoring, and / or deodorizing / masking composition according to any one of claims 9 to 10, wherein the content of the compound of formula (A, B, or C) is less than 50 wt.% or less than 25 wt.%.

12. The aromatic, flavoring, and / or deodorizing / masking composition according to any one of claims 9 to 11, comprising at least one ester and / or one alcohol, or at least a mixture of esters and alcohols, wherein the total content of the compound of formula (A, B, or C) together with the ester and / or alcohol is greater than 25 wt.% or greater than 50 wt.%.

13. Use of the aromatic, flavoring, and / or deodorizing / masking composition according to any one of claims 9 to 12 in a flavored or flavoring product.

14. Use of the compound or mixture according to any one of claims 1 to 8 in flavoring or seasoning products.

15. A method for preparing a compound of formula A, B, or C by reacting an olefin P selected from β-pinene, α-pinene, camphene, or δ-3-carene with an acceptor molecule, according to the following diagram. 。 16. The method for preparing a compound of formula A, B or C according to claim 15, wherein the reaction occurs in the presence of a tri(acetylacetone)ferric(III) catalyst abbreviated as Fe(acac)3.

17. A method for preparing a compound of formula (A, B, or C) according to any one of claims 15-16, wherein the reaction is carried out in the presence of a diol such as ethylene glycol and / or another solvent such as ethanol, propanol, and / or THF.

18. The method for preparing a compound of formula (A, B or C) according to any one of claims 15-16-17, wherein the preparation is carried out at a temperature of 50 to 65°C or 55 to 60°C.

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