Cyclohexene derivatives having organoleptic properties

Abstract

A compound which may be for use in perfumery or organoleptic applications is provided, where the compound has a general chemical Formula (I), where R1 is selected from H or CH3; and R2 is selected from the group consisting of H, CH3, and CH2CH=CH2. Methods of making and using same are further provided.

Description

CYCLOHEXENE DERIVATIVES HAVING ORGANOLEPTIC PROPERTIESFIELD OF THE INVENTION

[0001] The present invention relates generally to organoleptic compounds, more specifically cyclohexene derivatives having organoleptic properties.BACKGROUND OF THE INVENTION

[0002] Heliotropine or piperonal (2H-1 ,3-benzodioxole-5-carbaldehyde; CAS No. 120- 57-0) has been commonly used in fragrances and artificial flavors since the early 1880s. Heliotropine has a sweet, floral and nutty scent, akin to vanilla or almond, along with balsamic undertones and a hint of spice and woodiness, and a quiet anisic quality to it. For these reasons, it is commonly used to add vanilla or almond nuances, and generally imparting anisic, balsamic, powdery, and floral aspects to a scent's character.

[0003] However, heliotropine has been found to be potentially reprotoxic (CMR category 1 B) and may soon be eliminated from fragrant compositions by many fragrance and flavor suppliers. Therefore, there is a need to find new molecule(s) having an anisic, almond, powdery smell.SUMMARY OF THE INVENTION

[0004] Certain aspects of the present disclosure are described in the appended claims. There are additional features and advantages of the subject matter described herein. They will become apparent as this specification proceeds. In this regard, it is to be understood that the claims serve as a brief summary of varying aspects of the subjectmatter described herein. The various features described in the claims and below for various embodiments may be used in combination or separately. For example, specified ranges may be inclusive of their recited endpoints, unless explicitly excluded. Any particular embodiment need not provide all features noted above, nor solve all problems or address all issues noted above.

[0005] According to embodiments of the present invention, a compound is provided, where the compound has a general chemical Formula (I):where R1is selected from H or CH3; and R2is selected from the group consisting of H, CH3, and CH2CH-CH2.

[0006] The above compound can be used in perfumery or organoleptic applications.

[0007] According to embodiments of the present invention, a composition comprising one or more compound having a general chemical Formula (I) is provided. Said composition may be a fragrance composition, a flavor composition, a pharmaceutical composition, a cosmetic composition, a cleaning composition, a food composition or an intermediate composition for the preparation of one of said compositions.

[0008] According to embodiments of the present invention, use of one or more compounds having a general chemical Formula (I) as a fragrancing agent, a flavoring agent, an odor neutralizing agent, or a taste-masking agent is provided.

[0009] According to embodiments of the present invention, a process for modifying the organoleptic properties of a substance, a composition or an article comprising at least one of the following steps: adding a compound of general chemical Formula (I) to saidsubstance, composition, or article, or applying a compound of general chemical Formula (I) to the surface of said article, is provided.

[0010] According to embodiments of the present invention, a method of synthesizing a compound is provided, where the compound has a general chemical Formula (I):where R1is selected from H or CH3; and R2is selected from the group consisting of H, CH3, and CH2CH=CH2, the method comprising: a) converting a ketone compound having a general chemical Formula (II):into an epoxide compound having a general chemical Formula (III):b) converting the epoxide compound having the general Formula (III) into an allylic alcohol compound having a general Formula (I) wherein R2is H; and optionally, converting the allylic alcohol compound into an allylic ether compound having a general Formula (I) where R3is CH3 or CH2CH=CH2.DETAILED DESCRIPTION

[0011] Unless otherwise explained, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the present specification, includingexplanations of terms, will control. The singular terms "a," "an," "at least one," and "the" include plural referents unless context clearly indicates otherwise. Similarly, the word "or" is intended to include "and" unless the context clearly indicates otherwise. The term "comprising" means "including;" hence, "comprising A or B" means including A or B, as well as A and B together.

[0012] Embodiments of the invention relate to new cyclohexene derivatives, said compounds having pleasant fragrance properties (such as anisic, balsamic, powdery, and / or floral profiles), their preparation process, as well as their uses in the chemical industry, and in particular in perfumery, flavorings, cosmetics, parapharmacy, in the detergent industry, as well as in food, said compounds having interesting organoleptic properties and a particular potency and persistence. As used herein, "organoleptic properties" include sensory properties of a given composition such as, but not limited to, mouthfeel, texture, taste, smell, visual appearance, consistency of the product and physical attributes of a substance that are considered pleasing to the individual consumer.

[0013] Thus, in accordance with an embodiment of the invention, a compound is provided, where the compound has a general chemical Formula (I):where R1is selected from H or CH3; and R2is selected from the group consisting of H, CH3, and CH2CH-CH2.

[0014] In an embodiment, R1in general Formula (I) is H, thereby providing 4- ethylcyclohex-1 -en-1 -yl derivative compounds having the general Formula (la):

[0015] In another embodiment, R1in general Formula (I) is CH3, thereby providing 4- propylcyclohex-1 -en-1 -yl derivative compounds having the general Formula (lb):

[0016] In another embodiment, R2in general Formula (I) is H, thereby providing allylic alcohol compounds having the general Formula (IV):

[0017] In yet another embodiment, R2in general Formula (I) is CH3 (methyl) or CH2CHCH=CH2 (allyl), such that the compounds having the general Formula (V) are allylic ethers:where R3is CH3 or CH2CH=CH.

[0018] In accordance with an embodiment, the compound having the general Formula (I) is selected from the group consisting of (4-propylcyclohex-1 -en-1 -yl)methanol; (4- ethylcyclohex-1 -en-1 -yl)methanol; 1 -(methoxymethyl)-4-propylcyclohex-1 -ene; 1 - (methoxymethyl)-4-ethylcyclohex-1 -ene; 1 -((allyloxy)methyl)-4-propylcyclohex-1 -ene; and 1 -((allyloxy)methyl)-4-ethylcyclohex-1 -ene.

[0019] According to embodiments of the present invention, a method of synthesizing the compound for use in perfumery or organoleptic applications, the compound having the general chemical Formula (I):where R1is selected from H or CH3; and R2is selected from the group consisting of H, CH3, and CH2CH=CH2, is provided, the method comprising: a) converting a ketone compound having a general chemical Formula (II):into an epoxide compound having a general chemical Formula (III):Step a) may be performed by cyclopropanating the ketone function with an epoxidation agent. Non-limiting examples of suitable epoxidation reagents include trimethylsulfoxonium salts with base, such as trimethylsulfoxonium iodide with potassium t-butoxide, which are commonly known for effecting the Corey-Chaykovsky epoxidation of ketones.

[0020] The method further includes: b) converting the epoxide compound having the general Formula (III) into an allylic alcohol having a general Formula (IV):Step b) may be performed by isomerizing the epoxide function. For example, treatment of the epoxide with Lewis (e.g., aluminum isopropoxide) or Bronstead acids (e.g., p- toluenesulfonic acid monohydrate) in polar aprotic solvents (e.g., dichloromethane or anisole) effects the rearrangement of the epoxide to the desired allylic alcohol.

[0021] The method may further include: c) optionally, converting the allylic alcohol (IV) into an allylic ether compound having a general chemical Formula (V):where R3is CH3 or CH2CH=CH2.Step c) may be performed by alkylating the alcohol functional group. For example, using standard Williamson ether synthesis conditions, such as reacting an organohalide, such as methyl iodide or allyl bromide, with a deprotonated alkoxide of the alcohol having the general Formula (IV) in an aprotic solvent, forms the desired ether.

[0022] According to embodiments of the present invention, use of one or more compounds having a general chemical Formula I as a fragrancing agent, a flavoring agent, an odor neutralizing agent, or a taste-masking agent is provided.

[0023] According to embodiments of the present invention, a composition comprising one or more compound of formula (I) is provided. Said composition can be for instance a fragrance composition, a flavoring composition, a pharmaceutical composition, a cosmetic composition, a cleaning composition, a food composition or an intermediate composition for the preparation of one of said compositions.

[0024] The effective amount of the compound(s) of general chemical Formula (I) incorporated into these compositions depends on the nature of said compositions, the desired odorous or flavoring effect, and the nature of other odorous or flavoring compounds possibly present. It is easily determined by those skilled in the art, and can vary in a very wide range, from 100 ppb to 99%. For example, in an embodiment, the compound(s) of general chemical Formula (I) may be incorporated into composition in an amount from 100 ppb to 99%, or from 0.0001% to 50%, in particular 0.01% to 30%, more particularly from 0.1% to 30%. The preceding percentages are expressed by weight relative to the total weight of the composition. The composition may further comprise one or more additional fragrancing substance.

[0025] The composition may further comprise a flavoring ingredient, a solvent, an excipient, an additive or a fixative.

[0026] Other fragrancing substances that can be used in combination with the compounds of the present invention may be natural products such as extracts, essential oils, absolutes, resinoids, resins, concretes etc., but also synthetic products such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, nitriles etc., including saturated or unsaturated, aliphatic, heterocyclic, or carbocyclic compounds. Such fragrancing substances are mentioned, for example, in S. Arctander, "Perfume and Flavor Chemicals" (Montclair, N.J., 1969), or in "Common Fragrance and Flavor Materials", Wiley-VCH, Weinheim, 2006. Finally, a plurality of compounds of general chemical Formula (I) can also be used in combination in the same composition.

[0027] In a particular embodiment, the compound(s) of general chemical Formula (I) may be used in combination with anisic aldehyde (4-methoxybenzaldehyde), anisicalcohol (4-methoxybenzyl alcohol), or a combination of anisic aldehyde and anisic alcohol.

[0028] Because of the pleasant smell they emit, the compounds of general chemical Formula (I) find many applications in perfumery. The term "perfumery" is used here in its general sense; it refers not only to traditional perfumery (alcoholic or not), but also to other areas in which the smell / fragrance of products is important. Reference may thus be made to perfumery compositions in the usual and traditional sense (such as perfume bases and concentrates, perfumes, colognes, eau de toilette, indoor air fresheners, home fragrances, scented candles and similar products), to topical compositions including cosmetic compositions (such as face and / or body creams, talcum powders, hair oils, shampoos, hair lotions, bath salts and oils, shower and / or bath gels, toilet soaps, antiperspirants and body deodorants, shaving lotions and creams, soaps, toothpastes, mouthwashes, ointments, and similar products), as well as cleaning products, in particular household cleaning products (such as detergents, detergents, fabric softeners, home air fresheners, home fragrances and similar products).

[0029] Thus, embodiments of the invention extend to a perfume composition comprising at least one compound of general chemical Formula (I). It may, in particular, be a composition of the traditional perfumery, a cosmetic composition, cleaning product, or a so-called "intermediate composition", intended to be used for the preparation of compositions, or finished products (including perfumes, cosmetics, cleaning products).

[0030] Such a perfume composition is generally prepared from a basic product, in which the compound or compounds of the invention are found to be incorporated. The basic product will be easily determined by those skilled in the art according to the compositionenvisaged and therefore the intended use. The composition of these basic products and the nature of their usual components, such as perfuming ingredient(s), flavoring ingredient(s), solvent(s), additive(s), fixative(s), and / or adjuvant (s), are well known to those skilled in the art.

[0031] A fixative is a base ingredient or blend that is utilized in perfumes to help the scent last longer. For example, fixatives can reduce the rate of evaporation of the more volatile materials in fragrance composition.

[0032] A non-limiting list of fixatives includes resinoids such as benzoin, labdanum, myrrh, olibanum, storax, and tolu balsam; terpenoids such as ambroxide ((3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan); polycyclic ketones such as civetone ((9Z)-cycloheptadec-9-en-1 -one) and muscone ((3R)-3- methylcyclopentadecan-1 -one); glycerin; Galaxolide (4,6,6,7,8,8-hexamethyl-1 , 3, 4, 6,7,8- hexahydrocyclopenta[g]isochromene); Iso E Super (1 -(1 ,2,3,4,5,6,7,8-octahydro- 2,3,8,8,-tetramethyl-2-naphthyl)ethan-1 -one); Orrisroot (Rhizoma iridis); benzyl benzoate; triethyl citrate; dipropylene glycol (DPG); ethyl hexyl glycerin; and Oud base.

[0033] The compounds used in these perfume compositions, in particular the compounds of the invention, may be incorporated into or on an inert support material. The carrier materials that can be used are many and varied, for example polar solvents, oils, greases, finely divided solids, cyclodextrins, maltodextrins, gums, resins, and any other carrier material known for such compositions (for example, soaps, candles, ointments, textiles, wipes, scented gels, or the like).

[0034] According to another embodiment of the invention, the composition is flavor composition comprising at least one compound of general chemical Formula (I) and atleast one other flavoring substance. For example, in one aspect, the flavor composition may be an ingestible product, such as a pharmaceutical composition or a composition which refers to a "food", an "edible composition" and / or a "food product". Said ingestible product preferentially relates, but is not limited to, products intended for human consumption, intended for animal feed (pets). Examples of pharmaceutical compositions may include tablets, granules, sirups, solutions, suspensions, capsules, powders. Examples of food products may include, but are not limited to, snacks, confectionery, plant materials, and meals that may or may not provide essential nutrients. Plant materials include cocoa, cocoa beans, coffee, coffee beans, and tea leaves or powder. Examples of food products include salad dressings, sauces, sauces, marinades, sticks, nutrition bars, pastries, breads, caramel, cooked cereals, meat products, poultry products, meat, poultry, poultry, fish, marine protein sources, beans, pasta, confectionery products, salty snacks, dairy products, cheeses, yogurt, butter, margarine, ready-to-eat cereals, condiments and sauces and beverages. In particular, the term "beverage" includes mixtures and concentrates, including, but not limited to, ready-to-drink alcoholic and nonalcoholic beverages and dry powdered beverages. Non-limiting examples of beverages include, but are not limited to, soft drinks, brewed beverages, dairy products, drinking yogurt, milk, coffee whitening agents, nutritional drinks, and the like. Non-limiting examples of animal feed may include, but are not limited to, pet food, such as dogs and cats; rodent food; livestock feed; cattle feed; horse feed; and the like. Other applications for the compounds of general chemical Formula (I) may also include tobacco products or tobacco-related products.

[0035] The present invention also relates to a process for modifying the organoleptic properties of a substance, a composition or an article comprising at least one of the following steps: adding a compound of general chemical Formula (I) to said substance, composition or article, or applying a compound of general chemical Formula (I) to the surface of said article.

[0036] In one embodiment, at least one compound of general chemical Formula (I) is used as a fragrancing agent, alone or in combination with at least one other fragrancing substance, and / or at least one solvent, and / or at least one adjuvant. The additional fragrancing substance(s), solvents and adjuvants are known to those skilled in the art who will be able to choose the most appropriate or the most appropriate according to the desired effect.

[0037] As used herein, the term "fragrancing agent" is used here to refer to any organoleptic compound that pleasantly stimulates the sense of smell.

[0038] The compounds according to the invention may particularly be used as a masking agent (also known as an odor neutralizing agent). As used herein, the term "masking agent" or "odor neutralizing agent" is meant to identify a characteristic of the compounds within the scope of the invention to reduce or eliminate the perception of a bad odor generated by one or more other molecules present in a composition or a product.

[0039] The compounds according to the invention may also be used as a taste-masking agent. As used herein, the term "taste-masking agent" is meant to disguise or mask the unpleasant taste of certain ingredients.

[0040] In another embodiment, at least one compound of general chemical Formula (I) is used as a flavoring agent, alone or in combination with at least one other flavoring substance, and / or at least one solvent, and / or at least one adjuvant.

[0041] The additional flavoring substance(s), solvents and adjuvants are known to those skilled in the art who will be able to choose the most appropriate or the most appropriate according to the desired effect. The solvents used not only allow an exact dosage of the compound according to the invention for food and beverages, but also facilitates a uniform distribution of the compound according to the invention in food and beverages. Suitable solvents may be hydrophilic solvents such as water, propylene glycol, glycerol, ethanol and triacetin or hydrophobic solvents such as vegetable oils, e.g. palm oil, soybean oil, rapeseed oil, sunflower oil, peanut oil, medium-chain triglycerides (MCTs). Medium-chain triglycerides are triglycerides based on aliphatic fatty acids comprising 6 to 12 carbon atoms.

[0042] By flavor is meant any use of the compounds of the invention for the flavoring of any liquid or solid foodstuff, human or animal, including beverages, dairy products, ice cream. The compounds of general chemical Formula (I) may further find use in tobacco products or tobacco-related products.

[0043] In particular, the compounds according to the invention can be used alone or in combination with taste-modulating compounds, which modify taste and sensory perceptions. In any case, the specificity of such taste-modulating compounds is that they do not exhibit noticeable taste and aromatic properties (without taste and aroma). Such aroma-altering compounds can be of synthetic or natural origin.

[0044] EXAMPLES

[0045] Compound 1 - [6-propyl-1 -oxaspiro[2.5]octane] : In a 500 mL flask are added trimethylsulfoxonium iodide (54.1 g, 246 mmol), potassium t-butoxide (27.6 g, 246 mmol), dimethyl sulfoxide (DMSO) (250 ml). The mixture is stirred for 30 min and is then slowly added to a solution of 4-propylcyclohexan-1 -one (30 g, 214 mmol) in DMSO (80 ml) at 55 °C. The mixture is stirred at 55 °C for 30 min and then poured into a mixture of saturated NH4CI (150 mL), ice (100 mL), and ethyl acetate (EtOAc) (200 mL). The aqueous phase is extracted with EtOAc (200 mL) and the organic layers are combined and washed with saturated NaHCOs (100 mL) and brine (100 mL). The organic phase is dried on anhydrous MgSO4, filtered, and concentrated. Distillation over PPG2000 (70 °C, 8 torr) gave 6-propyl-1 -oxaspiro[2.5]octane (17.51 g, 112 mmol, 52.5 % yield) as a mixture of 2 isomers (90 / 10) in the form of a colorless liquid.MS (EI+) m / z : major isomer: 154 (2) [M+], 125 (54), 11 (52), 107 (10), 98 (24), 97 (14), 95 (14), 93 (17), 91 (15), 84 (100), 83 (28), 81 (41 ), 79 (41 ), 77 (22), 69 (27), 68 (13), 67 (46), 65 (10), 57 (11 ), 55 (74), 54 (38), 53 (31 ), 43 (82), 42 (13), 41 (84), 40 (10), 39 (40).1H NMR (300 MHz, Chloroform-d) 5 2.63 (s, 2H), 1.96 - 1.64 (m, 4H), 1.46 - 1.04 (m, 9H), 0.90 (t, J = 7.1 Hz, 3H).13C NMR (75 MHz, Chloroform-d) 5 58.57, 53.95, 38.92, 36.09, 32.73, 30.35, 20.06, 14.36. IR (cm1) : 915, 3031. Odor : fruity, green, buttery, pineapple.

[0046] Compound 2 - [(4-propylcyclohex-1 -en-1 -yl)methanol] : In a 250 mL round bottomed flask equipped with a distillation apparatus are added 6-proyl-1 - oxaspiro[2.5]octane (Compound 1 ; 23.77 g, 0.154 mol, 1.00 eq), anisole (157 mL) and aluminium isopropoxyde (3.847 g, 0.019 mol, 0.122 eq). The mixture is refluxed 3 h20 while collecting the distillate formed and then cooled down and quenched with 10%aqueous HCI (35 mL). Aqueous phase is extracted with anisole (2 x 60 mL) and the gathered organic phases are washed with sat. NaHCOs (20 mL), brine (20 mL), dried on anhydrous MgSCU, filtered and concentrated. Vacuum distillation (55 °C, 0.2 mbar) furnished (4-propylcyclohex-1 -en-1 -yl)methanol (16.30 g, 0.100 mol, 64.9%) as a colorless liquid.MS (EI+) m / z : 154 [Ml+(13), 136 (35), 123 (10), 108 (12), 107 (53), 105 (17), 95 (11 ), 94 (23), 93 (100), 92 (11 ), 91 (55), 83 (12), 81 (26), 80 (17), 79 (52), 78(10), 77 (43), 69 (11 ), 67 (29), 65 (12), 55 (25), 53 (10), 41 (23), 39 (15).1H NMR (300 MHz, CDCI3) 5 5.73 - 5.59 (m, 1 H), 3.97 (s, 2H), 2.24 - 1 .98 (m, 3H), 1 .93 (s, 1 H), 1 .86 - 1 .71 (m, 1 H), 1 .71 - 1 .57 (m, 1 H), 1 .57 - 1 .42 (m, 1 H), 1 .42 - 1 .07 (m, 5H), 0.90 (t, J= 7.1 Hz, 3H).13C NMR (75 MHz, CDCI3) 5 137.44, 122.52, 67.29, 38.74, 33.22, 31.70, 28.92, 25.72, 20.05, 14.33. IR (cm-1) : 3312, 1676. Odor : powerful, anisic, green, powdery, almond.

[0047] Compound 3 - [6-ethyl-1 -oxaspiro[2.5]octane] : In a 500 mL flask are added trimethylsulfoxonium iodide (60.2 g, 273 mmol), potassium t-butoxide (30.7 g, 273 mmol), DMSO (250 ml). The mixture is stirred for 30 min and is then slowly added over a solution of 4-ethylcyclohexan-1 -one (30 g, 214 mmol) in DMSO (80 ml) at 55 °C. The mixture is stirred at 70 °C for 30 min and then poured into a mixture of saturated NH4CI (150 mL), ice (100 mL) and EtOAc (200 mL). The aqueous phase is extracted with EtOAc (200 mL) and the organic layers are combined and washed with sat NaHCOs (100 mL) and brine (100 mL). The organic phase is dried on anhydrous MgSO4, filtered and concentrated. Distillation (82-84 °C, 24 torr) gave 6-ethyl-1 -oxaspiro[2.5]octane (18.61 g, 129 mmol, 54 % yield) as a mixture of 2 isomers (90 / 10) in the form of a colorless liquid.MS (EI+) m / z : major isomer: 140 (2) [M+] , 1 12 (1 1 ), 111 (100), 95 (12), 93 (14), 91 (10), 84 (95), 83 (18), 81 (38), 79 (38), 77 (20), 69 (32), 67 (40), 55 (61 ), 54 (41 ), 53 (29), 43 (73), 42 (11 ), 41 (74), 40 (11 ), 39 (44).1H NMR (300 MHz, Chloroform-d) 5 2.63 (s, 2H), 1.97 - 1.65 (m, 4H), 1.41 - 1.12 (m, 7H), 0.91 (t, J = 7.1 Hz, 3H).13C NMR (75 MHz, Chloroform-d) 5 58.57, 53.95, 38.14, 32.72, 29.98, 29.27, 11.56. IR (cm1) : 917, 3031. Odor : mushroom, ethereal, anisic, solvent.

[0048] Compound 4 - [(4-ethylcyclohex-1 -en-1 -yl)methanol] : In a round bottomed flash equipped with a distillation apparatus are added 6-ethyl-1 -oxaspiro[2.5]octane (Compound 3; 77.00 g, 0.549 mol, 1.00 eq), anisole (440 mL) and aluminium isopropoxyde (6.160 g, 0.030 mol, 0.055 eq). The mixture is refluxed 4 h while collecting the distillate formed and then cooled down and quenched with 10% aqueous HCI (100 mL). Aqueous phase is extracted with anisole (2 x 55 mL) and the gathered organic phases are washed with sat. NaHCOs (50 mL), brine (50 mL), dired on anhydrous MgSCU, filtered and concentrated. Vacuum distillation (54 °C, 0.3 mbar) furnished (4- ethylcyclohex-1 -en-1 -yl)methanol (39.100 g, 0.262 mol, 47.7%) as a colorless liquid.MS (EI+) m / z : 140 (32) [M+], 122 (19), 109 (37), 107 (30), 95 (17), 94 (25), 93 (100), 91 (35), 83 (22), 81 (20), 80 (11 ), 79 (47), 78 (10), 77 (38), 70 (15), 69 (16), 67 (57), 65 (13), 57 (15), 56 (19), 55 (56), 53 (19), 51 (11 ), 43 (19), 42 (1 1 ), 41 (56), 39 (33).1H NMR (300 MHz, Chloroform-d) 5 5.63 (ddt, J = 6.0, 3.2, 1.5 Hz, 1 H), 4.03 - 3.88 (m, 2H), 2.44 (s, 1 H), 2.21 - 2.12 (m, 2H), 2.13 - 1.96 (m, 2H), 1.86 - 1.53 (m, 2H), 1.46 - 1.09 (m, 3H), 0.90 (t, J = 7.3 Hz, 3H).13C NMR (75 MHz, Chloroform-d) 5 137.40, 122.45, 67.21 , 35.29, 31.36, 28.52, 26.89, 25.70, 11.47. IR (cm1) : 1678 (C=C), 3326 (O-H). Odor : Almond, anisic, powdery, coumarin.

[0049] Compound 5 - [1 -(methoxymethyl)-4-propylcyclohex-1 -ene] : In a round bottomed flask under nitrogen and equipped with a condenser are added sodium hydride 60% in mineral oil (0.933 g, 0.023 mol, 1.200 eq), THF (30.0 mL) and (4-propylcyclohex- 1 -en-1 -yl)methanol (Compound 2; 3.000 g, 0.019 mol, 1.000 eq) is added dropwise. The mixture is stirred at room temperature 1 h30 and methyl iodide (1.5 mL, 0.023 mol, 1.200 eq) is added. The mixture is then refluxed for 1 h and cooled down. Water (20 mL) is added, and the aqueous phase is extracted with MTBE (20 mL). The organics phases are gathered, washed with brine (20 mL), dried over anhydrous MgSC , filtered and concentrated. Distillation (44 °C, 0.3 mbar) yielded 1 -(methoxymethyl)-4-propylcyclohex- 1 -ene (1.200 g, 0.007 mol, 33.7%) as a colorless liquid.MS (EI+) m / z = 168 [M+] (46), 136 (26), 125 (18), 123 (20), 121 (15), 109 (10), 108 (22), 107 (62), 105 (10), 97 (38), 95 (19), 94 (30), 93 (100), 92 (12), 91 (55), 85 (15), 84 (24), 83 (1 1 ), 81 (48), 80 (23), 79 (83), 78 (13), 77 (49), 71 (23), 69 (18), 68 (22), 67 (70), 66 (10), 65 (19), 55 (34), 53 (26), 45 (67), 43 (18), 41 (82), 39 (43).1H NMR (300 MHz, Chloroform-d) 5 5.87 - 5.49 (m, 1 H), 3.77 (s, 2H), 3.28 (s, 3H), 2.23 - 2.07 (m, 1 H), 2.07 - 1.98 (m, 2H), 1.85 - 1.73 (m, 1 H), 1.72 - 1.40 (m, 1 H), 1.36 - 1.18 (m, 5H), 0.89 (t, J = 7.1 Hz, 3H).13C NMR (75 MHz, Chloroform-d) 5 134.74, 124.71 , 77.15, 57.53, 38.73, 33.15, 31.79, 28.90, 25.94, 20.04, 14.31. IR (cm1): 1086-1101 (C-O-C). Odor : powerful, anisic, green, earthy.

[0050] Compound 6 - [1 -((allyloxy)methyl)-4-propylcyclohex-1 -ene] : In a round bottomed flask under nitrogen and equipped with a condenser are added sodium hydride 60% in mineral oil (0.933 g, 0.023 mol, 1.200 eq), THF (30.0 mL) and (Compound 2; 4- propylcyclohex-1 -en-1 -yl)methanol (3.000 g, 0.019 mol, 1 .000 eq) is added dropwise. Themixture is stirred at room temperature 1 h30 and allyl chloride (1.9 mL, 0.023 mol, 1.200 eq) is added. The mixture is then refluxed for 48 h and cooled down. Water (20 mL) is added, and the aqueous phase is extracted with MTBE (20 mL). The organics phases are gathered, washed with brine (20 mL), dried over anhydrous MgSC , filtered and concentrated. Distillation (66-68 °C, 0.4 mbar) yielded 1-((allyloxy)methyl)-4- propylcyclohex-1 -ene (2.45 g, 62%) as a colorless liquid.MS (EI+) m / z : 194 [M+] (2), 151 (3), 138 (16), 136 (12), 123 (20), 110 (12), 109 (37), 107 (21 ), 107 (14), 96 (19), 95 (37), 95 (32), 94 (18), 94 (10), 93 (81 ), 91 (43), 83 (14), 81 (41 ), 81 (28), 80 (12), 79 (92), 77 (55), 69 (22), 68 (16), 67 (46), 67 (25), 65 (20), 57 (20), 55 (40), 55 (30), 53 (34), 51 (15), 44 (11 ), 43 (21 ), 43 (16), 42 (11 ), 41 (67), 41 (100), 40 (24), 40 (22), 39 (77).1H NMR (300 MHz, Chloroform-d) 5 5.93 (ddt, J = 17.2, 10.4, 5.6 Hz, 1 H), 5.74 - 5.60 (m, 1 H), 5.27 (dq, J = 17.2, 1 .7 Hz, 1 H), 5.22 - 5.07 (m, 1 H), 3.93 (dt, J = 5.6, 1 .4 Hz, 2H), 3.85 (s, 2H), 2.24 - 1 .90 (m, 3H), 1 .88 - 1 .72 (m, 1 H), 1 .72 - 1 .41 (m, 1 H), 1 .41 - 0.97 (m, 6H), 0.90 (t, J - 7.1 Hz, 3H).13C NMR (75 MHz, Chloroform- d) 5 135.06, 134.81 , 124.60, 116.69, 74.68, 70.66, 38.76, 33.16, 31.81 , 28.91 , 26.05, 20.04, 14.33. IR (cm-1): 917-989, 1081 , 1647. Odor : green, coriander, metallic, slightly anisic.

[0051] Compound 7 - [4-ethyl-1 -(methoxymethyl)cyclohex-1 -ene] : In a round bottomed flask under nitrogen and equipped with a condenser are added sodium hydride 60% in mineral oil (1 .997 g, 0.05 mol, 1 .400 eq), THF (92 mL) and (4-ethylcyclohex-1 -en- 1 -yl)methanol (Compound 4; 5.000 g, 0.036 mol, 1.000 eq) is added dropwise. The mixture is stirred at room temperature 1 h and methyl iodide (2.4 mL, 0.039 mol, 1.100 eq) is added. The mixture is then refluxed for 3 h and cooled down. Water (50 mL) andMTBE (30 mL) are added, and the organic phase is dried over anhydrous MgSO4, filtered and concentrated. Distillation (24 °C, 0.3 mbar) yielded 4-ethyl-1 -(methoxymethyl)cyclohex-l -ene (1.7 g, 27%) as a colorless liquid.MS (EI+) m / z : 154 (29), 125 (10), 122 (29), 109 (19), 107 (23), 97 (19), 95 (11 ), 94 (23), 93 (100), 91 (39), 84 (1 1 ), 81 (15), 80 (12), 79 (48), 77 (34), 71 (13), 68 (12), 67 (45), 65 (10), 55 (17), 53 (11 ), 45 (23), 41 (22), 39 (14).1H NMR (300 MHz, Chloroform-d) 5 5.72 - 5.61 (m, 1 H), 3.84 - 3.73 (m, 2H), 3.29 (s, 3H), 2.25 - 1.96 (m, 3H), 1.85 - 1.74 (m, 1 H), 1.74 - 1.60 (m, 1 H), 1.48 - 1.35 (m, 1 H), 1.34 - 1.16 (m, 3H), 0.91 (t, J = 7.4 Hz, 3H).13C NMR (75 MHz, Chloroform-d) 5 134.75, 124.69, 77.14, 57.51 , 35.25, 31.47, 29.04, 28.52, 25.95, 11.49. IR (cm1): 1673, 2851 , 2873, 2915. Odor : green, anisic, fruity, apple.

[0052] TABLE 1 : Fragrance Formulations

[0053] Trials versus anisic notes were evaluated: A floral mimosa accord (floral green anisic powdery accord) with heliotropine / anisic aldehyde / anisic alcohol was tested by replacing heliotropine with Compound 4 and keeping anisic aldehyde or anisic alcohol replacing the trio of anisic notes by only Compound 4. The floral mimosa accord was prepared according to Accord A, with commonly used heliotropine, anisic alcohol, and anisic aldehyde. By replacing these combined ingredients with Compound 4, we obtained Accord B. Accords C & D were obtained by removing Heliotropine, only one ingredient from the 2 others (anisic aldehyde or anisic alcohol, respectively) was kept in combination with Compound 4.

[0054] The different accords and effects were evaluated at 0.6% in a shampoo base, 1% in a softener base and 5% in alcohol (see Table 2).

[0055] Table 2: Application evaluations of Accords A-D.

[0056] As a conclusion, Compound 4 can interestingly substitute heliotropine. In particular, compound 4 performed especially well with anisic alcohol to impart a fusing powdery-green note.

[0057] While the invention has been illustrated by the description of one or more embodiments thereof, and while the embodiments have been described in considerable detail, they are not intended to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative product and / or method and examples shown and described. The various features of exemplary embodiments described herein may be used in any combination. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept.

Claims

CLAIMS1 . A compound having a general chemical formula (I):where R1is selected from H or CH3; and R2is selected from the group consisting of H, CH3, and CH2CH-CH2.

2. The compound according claim 1 , wherein R1is H.

3. The compound according to claim 1 , wherein R1is CH3.

4. The compound according to any one of claims 1 to 3, wherein R2is H.

5. The compound according to any one of claims 1 to 3, wherein R2is CH3.

6. The compound according to any one of claims 1 to 3, wherein R2is CH2CH=CH2.

7. The compound according to claim 1 , selected from the group consisting of (4- propylcyclohex-1 -en-1 -yl)methanol; (4-ethylcyclohex-1 -en-1 -yl)methanol; 1 - (methoxymethyl)-4-propylcyclohex-1 -ene; 1 -(methoxymethyl)-4-ethylcyclohex-1 -ene; 1 - ((allyloxy)methyl)-4-propylcyclohex-1 -ene; and 1 -((allyloxy)methyl)-4-ethylcyclohex-1 - ene.

8. A composition comprising one or more compound according to any one of claims 1 to 7, said composition being in particular a fragrance composition, a flavor composition, a pharmaceutical composition, a cosmetic composition, a cleaning composition, a food composition or an intermediate composition for the preparation of one of said compositions.

9. The composition of claim 8, wherein the composition further comprises one or more additional fragrancing substance.

10. The composition according to claim 9, wherein the one or more additional fragrancing substance is selected from 4-methoxylbenzaldehyde, 4-methoxylbenzyl alcohol, or both.11 . The composition according to any one of claims 1 to 7, wherein the composition further comprises a flavoring substance, a solvent, an excipient, an additive, or a fixative.

12. The composition according to any one of claims 8 to 11 , wherein the one or more compound having the general chemical formula (I) is present in a concentration of between 100 ppb and 99% by weight relative to the total weight of the fragrance composition, in particular from 0.0001 % to 50 % by weight, more particularly from 0.01 % to 30 % by weight, more particularly between 0.1 % and 30% by weight relative to the total weight of the composition.

13. Use of the compound according to any one of claims 1 to 7 as a fragrancing agent, a flavoring agent, an odor neutralizing agent, or a taste-masking agent.

14. A process for modifying the organoleptic properties of a substance, a composition or an article comprising at least one of the following steps: adding the compound according to any one of claims 1 to 7 to said substance, composition or article, or applying the compound according to any one of claims 1 to 7 to the surface of said article.

15. A method of synthesizing a compound having a general chemical formula (I):where R1is selected from H or CH3; and R2is selected from the group consisting of H, CH3, and CH2CH=CH2, the method comprising: converting a ketone compound having a general chemical Formula (II): Were Rijs se|ected from H or CH3 i ound having a general chemical Formula (III):converting the epoxide compound of formula (III) into an allylic alcohol compound having the general chemical formula (I) wherein R2is H; andoptionally, converting the allylic alcohol into an allylic ether compound having the general chemical formula (I), where R2is CH3 or CH2CH=CH2.

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