Cyclohexenylpropionaldehyde derivatives as perfuming ingredients

Abstract

The present invention relates to compounds of formula (I) in the form of any one of their stereoisomers, regioisomers or mixtures thereof. The use of the compounds of formula (I) as floral-type perfuming ingredients and the present compounds as part of a perfuming composition or of a perfuming consumer product are also part of the present invention.

Description

Technical Field

[0001] This invention relates to the field of fragrances (cosmetic flavorings). More specifically, this invention relates to the use of compounds of formula (I) as flavoring ingredients, which are particularly useful floral flavoring ingredients. Furthermore, this invention relates to flavored compositions or flavored consumer products containing compounds of formula (I). Background Technology

[0002] One of the key ingredients in the fragrance industry is the component that imparts a floral impression, especially the scent of lily of the valley. This fragrance is very popular and used in a variety of scented consumer products. (2-Methyl-3-[4-(2-methyl-2-propyl)phenyl]propanal, a trademark of Givaudan-Roure SA in Vergne, Switzerland) and (4 / 3-(4-hydroxy-4(methylpentyl)-3-cyclohexene-1-carboxaldehyde; source: International Flavors & Fragrances, USA) are commonly used ingredients for this purpose. It has the scent of lily of the valley and a watery quality, while It imparts a floral, lily-of-the-valley, and hydroxycitronellol fragrance, along with... The fragrance notes are completely different. However, both ingredients are restricted for various reasons.

[0003] Therefore, there is always a need to develop novel fragrance ingredients that impart floral notes, especially lily of the valley.

[0004] A related structural analog of the compound of formula (I) has been reported as a fragrance ingredient in WO 2017009175, characterized by a pleasant and well-balanced floral, lily of the valley, and hydroxycitronellol odor profile, while the overall olfactory characteristics strongly evoke one of the most familiar ingredients. The analogue is 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal, which has an aromatic phenyl moiety, i.e., a different chemical structure from the compound of the present invention.

[0005] No prior art literature reports on compounds of formula (I), nor suggests any sensory properties of such compounds, or any use of said compounds in the field of fragrance. Summary of the Invention

[0006] This invention relates to compounds of formula (I) that impart a floral, particularly lily-of-the-valley (also known as valley lily) scent, which is very popular in the fragrance industry.

[0007] The first objective of this invention is the compound of formula (I).

[0008]

[0009] The compound is in the form of any of its stereoisomers, regioisomers, or mixtures thereof.

[0010] A second object of the present invention is a method for imparting, enhancing, improving or altering the odor characteristics of a flavored composition or a flavored article, the method comprising adding an effective amount of at least one compound of formula (I) as defined above to the composition or article.

[0011] A third object of the present invention is the use of the compound of formula (I) as defined above as a flavoring ingredient.

[0012] Another object of the present invention is a flavoring composition comprising:

[0013] i) at least one compound of formula (I) as defined above;

[0014] ii) at least one ingredient selected from the group consisting of a fragrance carrier and a fragrance base; and

[0015] iii) Optionally, at least one flavoring adjuvant.

[0016] The final object of the present invention is a flavored consumer product comprising at least one compound of formula (I) or a composition as defined above. Detailed Implementation

[0017] Surprisingly, it has now been discovered that the compound of formula (I) has floral, lily of the valley and lilac scents, and imparts a floral-green, rose and ozone fragrance to the scented composition, which is particularly commendable.

[0018] The first objective of this invention is the compound of formula (I).

[0019]

[0020] The compound is in the form of any of its stereoisomers, regioisomers, or mixtures thereof. The compound can be used as a fragrance ingredient to impart floral, lily-of-the-valley, and lilac scents. The compound can also be used as a fragrance ingredient to impart floral-green, rose, and ozone-like notes, for example.

[0021] For clarity, the statement "any stereoisomer, regioisomer or mixture thereof" means that the compounds of the present invention can be "any stereoisomer or mixture thereof" and / or "any regioisomer or mixture thereof".

[0022] For clarity, the expression "any of its stereoisomers or mixtures thereof" or similar terms are used to indicate the normal meaning understood by those skilled in the art, namely that the compounds of the present invention can be pure enantiomers, mixtures of enantiomers or racemates.

[0023] For clarity, the phrase “any of its regioisomers or mixtures thereof” means in the normal sense understood by those skilled in the art that the propanal moiety linked to the olefinic double bond can replace any of the carbon atoms on the olefinic double bond of the compound of formula (I).

[0024] According to any of the above embodiments, the compound of the present invention has the following formula:

[0025]

[0026] The compound is in the form of any of its stereoisomers or mixtures thereof.

[0027] In other words, according to any of the above embodiments of the present invention, the compound of formula (I) may be selected from 3-(4-(2-hydroxy-2-methylpropyl)cyclohex-1-en-1-yl)propanal.

[0028] As a specific example, and as a non-limiting example, 3-(4-(2-hydroxy-2-methylpropyl)cyclohex-1-en-1-yl)propanal can be cited, which has a floral-green, rose, and ozone-like sensory impression.

[0029] When the odor of the compounds of the present invention is compared with that of the prior art compound 3-[4-(2-(2-hydroxy-2-methylpropyl)phenyl]propanal, the compounds of the present invention also have floral, lily-of-the-valley, and lilac odors, but impart a more floral-green, rose, and ozone sensory impression to the scented composition. In contrast to the prior art, the compounds of the present invention are very harmonious with green and rose scents.

[0030] According to any of the above embodiments of the present invention, the compound of formula (I) can be a mixture of regioisomers of the compound of formula (I), particularly and A mixture of regioisomers. According to a specific embodiment of the invention, the mixture of regioisomers is in the form of 90–50:10–50, more preferably 80–60:20–40, and even more preferably 75–65:25–35. The weight ratio is used.

[0031] As described above, the present invention relates to the use of compounds of formula (I) as fragrance ingredients. In other words, it relates to a method or process for imparting, enhancing, improving, or altering the odor characteristics of a fragrance composition, a fragranced article, or a surface, the method comprising adding an effective amount of at least one compound of formula (I) to said composition or article, for example, to convey its typical fragrance notes. It should be understood that the final pleasurable effect may depend on the precise dosage and sensory characteristics of the compounds of the present invention, but the addition of the compounds of the present invention will, depending on the dosage, impart a typical tactile quality to the final product in terms of fragrance notes, texture, or form.

[0032] By “use of the compound of formula (I)”, it must also be understood here as the use of any composition containing the compound of formula (I) and which can be advantageously used in the fragrance industry.

[0033] In fact, the composition described herein is also an object of the present invention as an advantageous flavoring ingredient.

[0034] Therefore, another object of the present invention is a flavoring composition comprising:

[0035] i) at least one of the compounds of the present invention as defined above, used as a flavoring ingredient;

[0036] ii) at least one ingredient selected from the group consisting of a fragrance carrier and a fragrance base; and

[0037] iii) Optionally, at least one flavoring adjuvant.

[0038] The term "fragrance carrier" refers to a material that is neutral from the perspective of fragrance, meaning it does not significantly alter the sensory properties of the flavoring ingredients. The carrier can be liquid or solid.

[0039] As liquid carriers, emulsion systems, i.e., solvent and surfactant systems, or solvents commonly used in fragrances, can be listed as non-limiting examples. A detailed description of the properties and types of solvents commonly used in fragrances is impossible to exhaust. However, solvents such as butanediol or propylene glycol, glycerol, dipropylene glycol and its monoethers, 1,2,3-propanetriyltriacetate, dimethyl glutarate, dimethyl adipate, 1,3-diacetoxypropyl-2-yl acetate, diethyl phthalate, isopropyl myristate, benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethanol, triethyl citrate, or mixtures thereof are the most commonly used. For compositions containing both fragrance carriers and fragrance bases, in addition to those detailed above, other suitable fragrance carriers may also be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins, such as those marketed under trademarks. Those known to the public (source: Exxon Chemical), or glycol ethers and glycol ether esters, such as those marketed under trademarks Those commonly known (source: Dow Chemical Company), or hydrogenated castor oil, such as those marketed as trademarks... RH 40, those that are well-known (Source: BASF).

[0040] A solid carrier is a material to which a flavoring composition or certain components of a flavoring composition can be chemically or physically bonded. Such solid carriers are typically used to stabilize compositions or to control the evaporation rate of compositions or certain components. Solid carriers are currently used in the art, and those skilled in the art know how to achieve the desired effects. However, as non-limiting examples of solid carriers, examples include absorbent resins or polymers or inorganic materials such as porous polymers, cyclodextrins, wood-based materials, organic or inorganic gels, clay, gypsum, talc, or zeolite.

[0041] Other non-limiting examples of solid carriers include encapsulating materials. Examples of such materials may include wall-forming and plasticizing materials, such as monosaccharides, disaccharides, or trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, proteins, or pectins, or as described in references such as H. Scherz, Hydrokolloide: Stabilisatoren, Dickungs- und Geliermittel in Lebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie, The materials listed in Behr's Verlag GmbH & Co., Hamburg, 1996. Encapsulation is a method well known to those skilled in the art and can be carried out, for example, by using techniques such as spray drying, agglomeration, or extrusion; or by encapsulation of coatings including agglomeration and composite agglomeration techniques.

[0042] As a non-limiting example of a solid carrier, a core-shell capsule may be specifically cited, which uses resins of the type of amino plastics, polyamides, polyesters, polyureas, or polyurethanes, or mixtures thereof (all of which are well known to those skilled in the art), and is carried out by a phase separation method initiated by using techniques such as polymerization, interfacial polymerization, coagulation, or these techniques together (all of which have been described in the prior art), and optionally in the presence of a polymer stabilizer or a cationic copolymer.

[0043] Resins can be produced by polycondensation of aldehydes (e.g., formaldehyde, 2,2-dimethoxyacetaldehyde, glyoxal, glyoxylic acid, or hydroxyacetaldehyde and mixtures thereof) with amines such as urea, benzoguanamine, glycoluryl, melamine, hydroxymethyl melamine, methylated hydroxymethyl melamine, guanidine, etc., and mixtures thereof. Alternatively, pre-formed resins can be used to alkylate polyamines, for example, under trademarks. (Source: Cytec Technology Corp.) (Source: Cytec Technology Corp.) or (Source: BASF) Those that are commercially available.

[0044] Other resins are produced by the formation of trimers from polyols such as glycerol and polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, or phenyl diisocyanate, or biuret of hexamethylene diisocyanate, or trimers of phenyl diisocyanate and trimethylolpropane (as trade name). Known, those produced by the condensation polymerization of (source: Mitsui Chemicals) in which phenyl diisocyanate is a trimer of trimethylolpropane and hexamethylene diisocyanate is a biuret.

[0045] Some research literature relating to the encapsulation of fragrances via the condensation of melamine resins with aldehydes includes articles such as those by K. Dietrich et al., Acta Polymerica, 1989, vol. 40, pages 243, 325, and 683, and 1990, vol. 41, page 91. These articles have described various parameters affecting the preparation of such core-shell microcapsules according to prior art methods, which are further detailed and exemplified in patent literature. Wiggins Teape Group Limited's US 4'396'670 is a relevant early example of the latter. Since then, many other authors have enriched the literature in this field, and it is impossible to cover all published advances here, but general knowledge of encapsulation techniques is essential. More recent targeted publications also address suitable uses of such microcapsules, such as the article by HY Lee et al., Journal of Microencapsulation, 2002, vol. 19, pages 559-569, and International Patent Publication WO01 / 41915 or S. The article by Chimia et al., 2011, vol. 65, pages 177-181, is representative.

[0046] The term "fragrance base" refers to a composition containing at least one flavoring ingredient.

[0047] The flavoring agent is not of formula (I). Furthermore, by "flavoring agent," this refers to a compound used in flavoring preparations or compositions to impart a pleasurable effect. In other words, for a substance to be considered a flavoring agent, it must be recognized by those skilled in the art as capable of actively or pleasantly imparting or altering the odor of a composition, and not merely possessing an odor.

[0048] The nature and type of fragrance additives present in the base material are not guaranteed to be described in greater detail here, and are inexhaustible in any case. Those skilled in the art can select them based on their common sense and according to the intended use or application and the desired sensory effect. Generally, these fragrance additives belong to different chemical classifications, such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenes, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils, and said fragrance additives may be of natural or synthetic origin.

[0049] In particular, examples of flavoring agents commonly used in fragrance preparations can be listed, such as:

[0050] - Aldehyde components: decanal, dodecanal, 2-methylundecaldehyde, 10-undecenal, octanal and / or nonenal;

[0051] -Aromatic herbal ingredients: eucalyptus oil, camphor, eucalyptol, menthol and / or α-pinene;

[0052] - Balsam ingredients: coumarin, ethyl vanillin and / or vanillin;

[0053] - Citrus flavoring components: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellol, orange terpene, limonene, 1-p-menthene-8-yl acetate and / or 1,4(8)-p-menthadiene;

[0054] - Floral fragrance components: Methyl dihydrojasmonate, linalool, citronellol, phenethyl alcohol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexylcinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, β-ionone, methyl 2-(methylamino)benzoate, (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, tricyclodecenyl acetate, geraniol, p-menth-1-en-8-ol, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate Mixtures of 1,1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, high-cis dihydrojasmonic acid methyl ester, 3-methyl-5-phenyl-1-pentanol, tricyclodecenyl propionate, geranyl acetate, tetrahydrolinalool, cis-7-p-menthol, (S)-2-(1,1-dimethylpropoxy)propionate, 2-methoxynaphthalene, 2,2,2-trichloro-1-phenylethyl acetate, 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde, pentylcinnamaldehyde, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, tricyclodecenyl isobutyrate, and / or methyl ionone isomers;

[0055] -Fruit flavor components: γ-undecyl lactone, 4-decyl lactone, ethyl 2-methylvalerate, hexyl acetate, ethyl 2-methylbutyrate, γ-nonyl lactone, allyl heptaate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-ethyl acetate and / or diethyl 1,4-cyclohexanedicarboxylate.

[0056] - Green fragrance components: 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styrax ester acetate, (2-methylbutoxy) allyl acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z)-3-hexen-1-ol and / or 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one;

[0057] -Musk components: 1,4-dioxa-5,17-cycloheptadecanedione, pentadecene lactone, 3-methyl-5-cyclopentadecanene-1-one, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[G]-2-benzopyran, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropyl ester, pentadecene lactone and / or (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methyl ester;

[0058] -Ingredients of costus root: 1-(octahydro-2,3,8,8-tetramethyl-2-naphthyl)-1-ethyl ketone, patchouli oil, terpene fraction of patchouli oil, (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, methyl cypressone, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol, 1-(2,3,8,8-tetramethyl-1,2,3,4,6,7,8,8a-octahydronaphthyl)ethyl-1-ketone and / or isobornyl acetate;

[0059] - Other components (e.g., amber, powdery, spicy, or watery): dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan and any stereoisomers thereof, piperaldehyde, anisaldehyde, eugenol, cinnamaldehyde, clove oil, 3-(1,3-benzodioxane-5-yl)-2-methylpropanal and / or 3-(3-isopropyl-1-phenyl)butanal.

[0060] The fragrance base according to the invention may not be limited to the aforementioned flavoring auxiliary ingredients, and many other such auxiliary ingredients are listed in the references in any case, such as S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or later versions thereof, or other works of similar nature, as well as a large number of patent documents in the fragrance industry. It should also be understood that the auxiliary ingredients may also be compounds known to release various types of flavoring compounds in a controlled manner.

[0061] By "fragrance adjuvants," we mean ingredients that can impart additional benefits such as color, specific lightfastness, chemical stability, etc. A detailed description of the properties and types of adjuvants commonly used in fragrance compositions is impossible to exhaust, but it must be mentioned that the ingredients are well known to those skilled in the art. Specific, non-limiting examples include: viscous agents (e.g., surfactants, thickeners, gelling and / or rheology modifiers), stabilizers (e.g., preservatives, antioxidants, heat / light or buffering agents or chelating agents, such as BHT), colorants (e.g., dyes and / or pigments), preservatives (e.g., antibacterial or antimicrobial or antifungal or antiirritant agents), abrasives, skin coolants, fixatives, insect repellents, ointments, vitamins, and mixtures thereof.

[0062] It is understood that those skilled in the art, by applying standard knowledge in the field and by mixing the above-mentioned components of the fragrance composition through trial and error, are fully capable of designing the optimal formulation for the desired effect.

[0063] In addition to flavoring compositions comprising at least one compound of formula (I), at least one flavor carrier, at least one flavor base and optionally at least one flavor adjuvant, compositions of the present invention consisting of at least one compound of formula (I) and at least one flavor carrier also constitute a specific embodiment of the present invention.

[0064] According to a particular embodiment, the above composition comprises more than one compound of formula (I), which enables perfumers to prepare blends or fragrances having scent notes of different compounds of the present invention, thereby creating new structural units for creative purposes.

[0065] For clarity, it should also be understood that any mixture obtained directly from chemical synthesis (where the material compositions of the present invention serve as starting materials, intermediates, or end products), such as reaction media that have not been adequately purified, cannot be considered a flavoring composition according to the present invention, provided that the mixture does not provide the compounds of the present invention in a suitable form for use in fragrances. Therefore, unless otherwise stated, unpurified reaction mixtures are generally excluded from the present invention.

[0066] The compounds of the present invention can also be advantageously used in all areas of modern fragrances (i.e., fine fragrances or functional fragrances) to actively impart or alter the odor of consumer products containing compounds of formula (I). Therefore, another object of the present invention is a scented consumer product comprising at least one compound of formula (I) as defined above as a scenting ingredient.

[0067] The compounds of the present invention may be added as is or as part of the fragrance composition of the present invention.

[0068] For clarity, a "fragrant consumer product" refers to a consumer product that delivers at least one pleasant fragrance effect to the surface or space on which it is applied (e.g., skin, hair, fabric, or household surfaces). In other words, a fragrant consumer product according to the invention is such a product comprising a functional formulation and optional additional benefit agents corresponding to the desired consumer product, and an olfactorily effective amount of at least one compound of the invention. For clarity, the fragrant consumer product is a non-edible product.

[0069] The nature and type of ingredients in flavored consumer products are not guaranteed to be described in more detail here, and in any case, they cannot be exhaustively described. Skilled workers can select them based on their common sense and the characteristics of the product and the desired effect.

[0070] Non-limiting examples of suitable scented consumer products include perfumes, such as fine perfumes, sprays, or eau de perfumes, colognes, or shaving lotions or aftershaves; fabric care products, such as liquid or solid detergents, fabric softeners, liquid or solid fragrance enhancers, fabric fresheners, ironing solutions, paper products, bleach, carpet cleaners, and curtain care products; body care products, such as hair care products (e.g., shampoos, colorants or hairsprays, color-correcting products, hair styling products, and dental care products), disinfectants, and feminine hygiene products; cosmetic preparations (e.g., skin creams or lotions, deodorants, or antiperspirants), hair removal products, tanning agents, or sunscreens. Or after-sun products, nail products, skin cleansing products, cosmetics); or skin care products (such as soaps, shower mousses, bath oils or bath gels, or hygiene products or foot / hand care products); air care products, such as air fresheners or "ready-to-use" powder air fresheners that can be used in home spaces (rooms, refrigerators, cabinets, shoes or cars) and / or public spaces (lobby, hotels, shopping malls, etc.); or household care products, such as mold removers, furniture conditioners, wipes, dishwashing liquids or hard surface cleaners (such as floors, bathrooms, sanitary ware or windows); leather care products; car care products, such as polishes, waxes or plastic cleaners.

[0071] Some of the aforementioned scented consumer products may represent corrosive media of the compounds of the present invention, and therefore may need to be protected from premature decomposition, for example by encapsulation or by chemically binding them to another chemical substance that is suitable for releasing the components of the present invention when subjected to suitable external stimuli, such as enzymes, light, heat or pH changes.

[0072] The compounds according to the invention can be incorporated into various of the above-described products or compositions in proportions that vary over a wide range of values. When the compounds according to the invention are mixed with flavoring agents, solvents, or additives commonly used in the art, these values ​​depend on the nature of the product to be flavored, the desired sensory effect, and the nature of the auxiliary ingredients in the given base.

[0073] For example, in the case of a flavored composition, the typical concentration of the compound of the present invention is 0.001% to 10% by weight, or even more, based on the weight of the composition to which it is incorporated. In the case of a flavored consumer product, the typical concentration of the compound of the present invention is 0.01% to 5% by weight, or even more, based on the total weight of the consumer product to which it is incorporated.

[0074] The compounds of the present invention can be prepared according to the methods described below.

[0075] Examples

[0076] The invention will now be described in further detail through the following embodiments, wherein abbreviations have their usual meanings in the art, and temperature is expressed in degrees Celsius (°C); used in (400MHz) 1 H) and 100MHz 13 Bruker AdvanceII Ultrashield 400plus operating at (C) or (500MHz) 1 H) and 125MHz 13 Bruker Advance III500plus operating at (C) or (600MHz) 1 H) and 150MHz 13 NMR spectra were obtained using a Bruker Advance III 600 cryoprobe operated under C) conditions. Spectra were used as an internal reference; chemical shift δ is expressed in ppm relative to TMS 0.0 ppm; and coupling constant J is expressed in Hz.

[0077] 3-(4-(2-hydroxy-2-methylpropyl)cyclohex-1-en-1-yl)propanal

[0078] Step 1: Ethyl 4-(4-methylpent-3-en-1-yl)cyclohex-3-en-1-carboxylate:

[0079] At 0°C, ethyl acrylate (27.1 mL, 250 mmol, 1 equivalent) was added dropwise to a suspension of aluminum trichloride (3.33 g, 25 mmol, 0.1 equivalent) in toluene (58 mL), followed by the addition of myrcene (47.3 mL, 275 mmol, 1.1 equivalent). The solution was slowly heated to room temperature and stirred at room temperature for 3 days. The mixture was then quenched with 5% HCl solution. The aqueous layer was removed, and the solution was extracted with diethyl ether. The organic phase was washed with saturated sodium bicarbonate solution, dried over sodium sulfate, filtered, and the solvent was evaporated under vacuum. The residue was ready for use in the next step without further purification.

[0080] Step 2: (4-(4-methylpent-3-en-1-yl)cyclohex-3-en-1-yl)methanol:

[0081] At 0 °C, a THF solution of ethyl 4-(4-methylpent-3-en-1-yl)cyclohexyl-3-en-1-carboxylate (from the crude product of the previous step, 250 mmol, 1 equivalent) in 100 mL was added dropwise to a THF (400 mL) suspension of lithium aluminum hydride (9.47 g, 250 mmol, 1 equivalent), while maintaining the temperature below 8 °C. After stirring at 0 °C for 1 hour, the reaction was quenched sequentially with 10 mL of water, 30 mL of 5% NaOH solution, and 10 mL of water. The suspension was filtered on a diatomaceous earth mat using diethyl ether as the eluent, and the solvent was evaporated under vacuum. The crude product was purified by ball-to-ball distillation (0.15–0.2 mbar, 130 °C) to give the desired alcohol as an oil (45.5 g, 94% overall yield of both steps).

[0082] 1 H NMR(CDCl3,600MHz):1.56(s,1H),1.60(s,3H),1.68(s,3H),1.70-1.77(m,2H),1.81-1.85(m,1H ),1.94-2.02(m,4H),2.05-2.12(m,3H),3.49-3.56(m,2H),5.08-5.11(m,1H),5.38-5.40(m,1H).

[0083] 13 C NMR(CDCl3,150MHz):137.8(s),131.4(s),124.4(d),119.5(d),67.8(t),3 7.7(t),36.4(d),28.2(t),27.8(t),26.5(t),25.7(q),25.7(t),17.7(q).

[0084] Step 3: Methyl methanesulfonate (4-(4-methylpent-3-en-1-yl)cyclohex-3-en-1-yl) ester:

[0085] At 0 °C, methanesulfonyl chloride (21.9 mL, 281 mmol, 1.2 equivalence) was added dropwise to a solution of (4-(4-methylpent-3-en-1-yl)cyclohex-3-en-1-yl)methanol (45.5 g, 234 mmol, 1 equivalent) and triethylamine (49.0 mL, 351 mmol, 1.5 equivalent) in dichloromethane (468 mL). The reaction was stirred at room temperature for 5 min and then quenched with saturated ammonium chloride solution. The mixture was extracted twice with diethyl ether, and the combined organic extracts were washed twice with brine, dried over sodium sulfate, filtered, and the solvent was evaporated under vacuum. The residue was ready for use in the next step without further purification.

[0086] Step 4: 4-(bromomethyl)-1-(4-methylpent-3-en-1-yl)cyclohexyl-1-ene:

[0087] Tetrabutylammonium bromide (91 g, 281 mmol, 1.2 equivalents) was added to a THF (586 mL) solution of methyl methanesulfonic acid (4-(4-methylpent-3-en-1-yl)cyclohex-3-en-1-yl) (from the crude product of the previous step, 234 mmol, 1 equivalent), and the reaction was refluxed for 18 hours. The solvent was evaporated, diethyl ether was added, the organic phase was washed twice with water and then with brine, dried over sodium sulfate, filtered, and the solvent was evaporated under vacuum. The residue was purified by ball-to-ball distillation (0.15–0.2 mbar, 135 °C) to give the desired bromide as an oil (57.7 g, 96% overall yield of both steps).

[0088] 1 H NMR(CDCl3,600MHz):1.34-1.41(m,1H),1.60(s,3H),1.68(s,3H),1.77-1.83(s,1H),1.8 6-2.10(m,8H),2.19-2.23(m,1H),3.36(d,J=6.5Hz,2H),5.07-5.10(m,1H),5.36(m,1H).

[0089] 13 C NMR (CDCl3, 150MHz): 137.6(s), 131.5(s), 124.2(d), 119.1(d), 39.7(t), 37.5(t), 36.1(d), 30.5(t), 27.8(t,2C), 26.4(t), 25.7(q), 17.7(q).

[0090] Step 5: 2-Methyl-1-(4-(4-methylpent-3-en-1-yl)cyclohex-3-en-1-yl)prop-2-ol:

[0091] A few drops of 4-(bromomethyl)-1-(4-methylpent-3-en-1-yl)cyclohex-1-ene were added to a suspension of magnesium shavings (5.99 g, 246 mmol, 1.1 equivalents) and two drops of 1,2-dibromoethane (catalytic amount) in THF (5 mL), and the mixture was refluxed. After initiation was observed, the remaining 4-(bromomethyl)-1-(4-methylpent-3-en-1-yl)cyclohex-1-ene (57.6 g, 224 mmol, 1 equivalent) in THF (220 mL) was added dropwise while maintaining reflux. After the addition was complete, the mixture was heated for approximately 20 minutes. The reaction was cooled to room temperature (partial precipitation occurred), and acetone (24.7 mL, 336 mmol, 1.5 equivalents) was added dropwise while maintaining the temperature below 25 °C. After stirring for 1 hour, a saturated ammonium chloride solution was added. The reaction mixture was extracted three times with diethyl ether. The combined organic extracts were dried over sodium sulfate, filtered, and the solvent was evaporated under vacuum. The residue was purified by silica gel rapid column chromatography (heptane / AcOEt 93:7) and subjected to ball-to-ball distillation (0.17–0.2 mbar, 125 °C) to give the desired alcohol as an oil (16.6 g, 31% yield).

[0092] 1 H NMR (CDCl3, 600MHz): 1.25 (s, 6H), 1.27-1.35 (m, 1H), 1.43 (A of ABX, J = 14.2, 5.4Hz, 1H), 1.48 (B of ABX,J=14.2,5.4Hz,1H),1.60(s,3H),1.68(s,3H),1.68-1.78(m,2H),1.79-1.83(m,1H), 1.93-1.95(m,3H),2.01-2.09(m,3H),2.17-2.20(m,1H),5.09-5.11(m,1H),5.36(m,1H).

[0093] 13 C NMR(CDCl3,150MHz):137.6(s),131.3(s),124.5(d),120.2(d),71.6(s),50.3(t),37.7( t),33.9(t),31.1(t),30.1(q),30.0(d),30.0(q),28.5(t),26.5(t),25.7(q),17.7(q).

[0094] Step 6: 3-Bromo-5-(4-(2-hydroxy-2-methylpropyl)cyclohex-1-en-1-yl)-2-methylpent-2-ol:

[0095] At 0 °C, a solution of NBS (17.4 g, 98 mmol, 1.5 equivalent) in the same solvent mixture (569 mL) was added dropwise to a solution of 2-methyl-1-(4-(4-(methylpent-3-en-1-yl)cyclohex-3-en-1-yl)prop-2-ol (15.4 g, 65 mmol, 1 equivalent) in THF (354 mL) and water (215 mL). The reaction was stirred at 0 °C for 1 hour, extracted twice with AcOEt, and the combined organic extracts were dried over sodium sulfate, filtered, and the solvent was evaporated under vacuum. The residue was ready for use in the next step without further purification.

[0096] Step 7: 1-(4-(2-(3,3-dimethylethyleneoxy-2-yl)ethyl)cyclohexyl-3-en-1-yl)-2-methylprop-2-ol:

[0097] Potassium carbonate (8.99 g, 65 mmol, 1 equivalent) was added to a methanol (260 mL) solution of 3-bromo-5-(4-(2-hydroxy-2-methylpropyl)cyclohex-1-en-1-yl)-2-methylpent-2-ol (the crude product from the previous step, 65 mmol, 1 equivalent), and the mixture was stirred at room temperature for 1 hour. The solution was diluted with water and extracted twice with diethyl ether. The combined organic extracts were dried over sodium sulfate, filtered, and the solvent was evaporated under vacuum. The residue was purified by silica gel rapid column chromatography (heptane / AcOEt 85:15 to 7:3) to give an oil, which was used directly in the next step.

[0098] Step 8: 3-(4-(2-hydroxy-2-methylpropyl)cyclohex-1-en-1-yl)propionaldehyde:

[0099] At 0 °C, periodic acid (17.8 g, 78 mmol, 1.2 equivalents) was added aliquots to a solution of 1-(4-(2-(3,3-dimethylethyleneoxy-2-yl)ethyl)cyclohexyl-3-en-1-yl)-2-methylprop-2-ol (from the previous step, 65 mmol, 1 equivalent) in THF (300 mL) and water (150 mL). The reaction was slowly heated to room temperature and stirred at room temperature for 30 minutes. Water was added, and the mixture was extracted twice with diethyl ether. The combined organic extracts were washed with 10% sodium thiosulfate solution, washed with brine, dried over sodium sulfate, filtered, and the solvent was evaporated under vacuum. The residue was purified by silica gel rapid column chromatography (heptane / AcOEt 8:2 to 7:3) and subjected to ball-to-ball distillation (0.17–0.2 mbar, 135 °C) to obtain the desired aldehyde as an oil (6.00 g), with an overall yield of 44% in three steps.

[0100] 1H NMR (CDCl3, 600MHz): 1.24 (s, 6H), 1.27-1.34 (m, 2H), 1.42 (A of ABX, J = 14.2, 5.4Hz, 1H), 1.48 (B of ABX,J=14.2,5.4Hz,1H),1.66-1.77(m,2H),1.81-1.85(m,1H),1.91-1.94(m,1H),2.01-2.06(m, 1H),2.17-2.20(m,1H),2.27-2.29(m,2H),2.51-2.54(m,2H),5.38(m,1H),9.76(t,J=1.8Hz,1H). 13 C NMR(CDCl3,150MHz):202.8(d),135.5(s),121.4(d),71.5(s),50.1(t),4 1.9(t),33.7(t),30.8(t),30.1(q),30.0(q),29.9(d),29.7(t),28.5(t).

[0101] Example 2

[0102] Preparation of a perfuming composition

[0103] The olfactory evaluation of 3-(4-(2-hydroxy-2-methylpropyl)cyclohex-1-en-1-yl)propanal obtained in Example 1 showed that it exhibited floral, lily-of-the-valley and lilac aromas.

[0104] To evaluate its role in the composition, a women's fragrance was prepared by mixing the following ingredients:

[0105]

[0106]

[0107] *In dipropylene glycol

[0108] 800 parts by weight of 3-(4-(2-hydroxy-2-methylpropyl)cyclohex-1-en-1-yl)propanal obtained in Example 1 were added to the above composition in place of 800 parts by weight of dipropylene glycol, giving the latter a floral-green, rose and ozone connotation.

[0109] When the same amount of 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal is used instead of 800 parts by weight of dipropylene glycol in place of the compounds of the present invention, the composition acquires a more floral-valley lily, more creamy and more powdery character.

[0110] When the same amount of 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal is used instead of 800 parts by weight of dipropylene glycol in place of the compounds of the present invention, the composition achieves a more rounded, floral-valley lily-like, fresher character, and possesses a similar... The moisturizing effect.

[0111] When replacing the compound of the present invention, using the same amount When replaced with 800 parts by weight of dipropylene glycol, the composition achieves a more rounded, floral-valley lily, fresher character, and a moisturizing effect.

[0112] 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal blends well with ozone, aqueous, and salicylate fragrances in fragrance compositions. 3-(4-(1-hydroxy-2-methylpropyl-2-yl)phenyl)propanal blends particularly well with salicylate and musk fragrances. The compound of the present invention, 3-(4-(2-hydroxy-2-methylpropyl)cyclohex-1-en-1-yl)propanal, blends particularly well with green, rose, and aqueous fragrances.

[0113] Example 3

[0114] Preparation of a perfuming composition

[0115] Men's fragrance is made by mixing the following ingredients:

[0116]

[0117]

[0118] *In dipropylene glycol

[0119] 800 parts by weight of 3-(4-(2-hydroxy-2-methylpropyl)cyclohex-1-en-1-yl)propanal obtained in Example 1 were added to the above composition in place of 800 parts by weight of dipropylene glycol, giving the latter a floral-green, rose and ozone connotation.

[0120] When the same amount of 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal is used instead of 800 parts by weight of dipropylene glycol in place of the compounds of the present invention, the composition acquires a more floral-valley lily, more creamy and more powdery character.

[0121] When the same amount of 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal is used instead of 800 parts by weight of dipropylene glycol in place of the compounds of the present invention, the composition achieves a more rounded, floral-valley lily-like, fresher character, and possesses a similar... The moisturizing effect.

[0122] When replacing the compound of the present invention, using the same amount When replaced with 800 parts by weight of dipropylene glycol, the composition achieves a more rounded, floral-valley lily, fresher character, and a moisturizing effect.

[0123] 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal mixes well with ozone, water, salicylate and oakmoss notes in fragrance compositions; 3-(4-(1-hydroxy-2-methylpropyl-2-yl)phenyl)propanal mixes particularly well with salicylate and musk notes; and the compound of the present invention, 3-(4-(2-hydroxy-2-methylpropyl)cyclohex-1-en-1-yl)propanal, mixes particularly well with green, rose and ozone notes.

Claims

1. Compound of formula (II), The compound is in the form of any of its stereoisomers or mixtures thereof.

2. A method for imparting, enhancing, improving or altering the odor characteristics of a flavored composition or a flavored article, the method comprising adding an effective amount of at least one compound of formula (II) as defined in claim 1 to the composition or article.

3. Use of the compound of formula (II) as defined in claim 1 as a flavoring ingredient.

4. A flavoring composition comprising: i) at least one compound of formula (II) as defined in claim 1; ii) at least one ingredient selected from the group consisting of a fragrance carrier and a fragrance base; and iv) Optionally, at least one spice adjuvant.

5. A flavored consumer product comprising at least one compound of formula (II) as defined in claim 1 or a composition as defined in claim 4.

6. The scented consumer product according to claim 5, characterized in that... This product is a perfume, fabric care product, body care product, cosmetic preparation, skin care product, air care product, or household care product.

7. The scented consumer product according to claim 6, characterized in that... The scented consumer products are fine perfumes, topical perfumes or eau de toilette, colognes, shaving lotion or aftershave, liquid or solid detergents, fabric softeners, fabric fresheners, ironing solutions, paper products, bleach, carpet cleaners, curtain care products, shampoos, colorants, color care products, hair styling products, dental care products, disinfectants, feminine hygiene products, hair sprays, cold creams, deodorants or antiperspirants, hair removal products, tanning or sun protection products, nail products, skin cleansers, cosmetics, soaps, bath mousses, bath oils or bath gels, or foot / hand care products, hygiene products, air fresheners, mildew removers, furniture care products, wipes, dishwashing liquids or hard surface cleaners, leather care products, or car care products.

8. The flavored consumer product according to claim 6, characterized in that... This scented consumer product is a "ready-to-use" powder air freshener.

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