NEW SPIROOXATHIOLANONE COMPOUNDS, THEIR PREPARATION PROCESS AND THEIR USE IN PERFUMERY AND AROMATICS

Description

[0001] The present invention relates to new spirooxathiolanone type compounds having fruity, peach and / or exotic fruit notes, their preparation process, as well as their uses in the chemical industry, and in particular in perfumery, cosmetics, parapharmacy, in the detergent industry, as well as in the food industry, said compounds having interesting organoleptic properties as well as particular potency and persistence.

[0002] To expand the range of notes available to perfumers and flavorists for their creations, the fragrance and flavor industry is constantly searching for new organoleptic compounds that meet both increasingly stringent regulatory requirements and those identified by legislators as undesirable or even unacceptable. Cost constraints are also becoming increasingly important.

[0003] Among organoleptic molecules, compounds with fruity, peach, and / or exotic fruit notes are few. The most commonly used compounds include gamma-undecalactone, Nectaryl® (Givaudan), and Apritone® (Bedoukian):

[0004] However, the compounds of the prior art and in particular those above present fruity and / or exotic fruit notes always accompanied by a fatty, lactonic, creamy side, which gives an unnatural aspect to the aroma or fragrance, which is not advantageous.

[0005] Furthermore, in order to meet the ongoing needs of the fragrance and flavor industry and to broaden the range of options available to perfumers and flavorists, the Applicant has identified new spirooxathiolanone compounds with a unique fruity note, such as peach and / or exotic fruits, which have the advantage of lending a natural character to compositions. These compounds possess sufficiently potent notes to allow for use at very low final concentrations in ready-to-use fragrance or flavor compositions.

[0006] These spirooxathiolanone compounds correspond to the following formula (I): in which: R1, R2, R3, R4, R6 and R7, independently represent a hydrogen atom or a methyl group; R5 represents a hydrogen atom or a saturated linear C1-C5 alkyl group; R4 and R5 can together form a cyclopentyl group; the total number of carbon atoms being strictly greater than 9.

[0007] The present invention also relates to a composition comprising at least one compound of general formula (I).

[0008] Furthermore, a third object of the present invention relates to a method for preparing a compound of general formula (I), said method being simple, advantageous in terms of yield, comprising a single step and therefore inexpensive.

[0009] Finally, a last object of the present invention relates to the use of at least one compound of general formula (I) to confer, modify or enhance the organoleptic properties of a substance, composition or article.

[0010] To the Applicant's knowledge, none of the compounds corresponding to the general formula (I) have been previously identified.

[0011] Spirolactone compounds used in perfumery have been identified in the prior art, such as in US patent 4519944 which discloses compounds with the following formula:

[0012] These compounds are not only structurally different from the compounds of the present invention, but they also exhibit (for the preferred compounds) woody, milky, lactonic, powdery notes, notes which are therefore quite different from the compounds described in the present invention.

[0013] Furthermore, scientific publications disclose certain spirooxathiolanone compounds but without identifying their organoleptic properties. Examples include 7-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one and 3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one (Tetrahedron, 1970, 26(19), 4641-4648) as well as 8-tert-butyl-1-oxa-4-thiaspiro[4.5]decan-2-one (Synth. Commun., 2003, 33(11), 1951-1961).

[0014] Finally, patent application JP 2001039972 (Hasegawa) describes oxathiolanones with a meaty, nutty, culinary odor, of the general formula: therefore far removed from the fruity, peach and / or exotic notes of the compounds described in the present invention.

[0015] The spirooxathiolane compounds of the present invention possess, on the one hand, a chemical structure that is distinct and novel from that of prior art compounds and, on the other hand, fruity, peach, and / or exotic fruit notes that lend a natural appearance to the compositions compared to the reference compounds. Furthermore, the compounds according to the invention have very low odor detection thresholds, particularly compared to the reference compound gamma-undecalactone. Also compared to gamma-undecalactone, the spirooxathiolane compounds of the present invention exhibit a significantly higher "odor value" (obtained by dividing the volatility by the odor detection threshold) than gamma-undecalactone, thus demonstrating the potency of said compounds compared to gamma-undecalactone.

[0016] Thus, the present invention relates to spirooxathiolanone compounds of the following general formula (I): in which: R1, R2, R3, R4, R6 and R7, independently represent a hydrogen atom or a methyl group; R5 represents a hydrogen atom or a saturated linear C1-C5 alkyl group; R4 and R5 can together form a cyclopentyl group; the total number of carbon atoms being strictly greater than 9.

[0017] For the purposes of the present invention, the term "C1-C5 alkyl" means any monovalent radical derived from a saturated, linear carbon chain containing 1 or 5 carbon atoms, i.e. a methyl, ethyl, propyl, butyl and pentyl group.

[0018] According to a first embodiment, R5 represents a saturated linear C1-C5 alkyl group. Preferably, R5 represents an ethyl or propyl group.

[0019] According to another preferred embodiment, R1, R2, R3, R4, R6 and R7 represent a hydrogen atom.

[0020] More specifically, the total number of carbon atoms is 10 or 11.

[0021] According to another preferred embodiment, the total number of carbon atoms is 12.

[0022] In a preferred embodiment, the compound according to the present invention is selected from 7,7-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-ethyl-3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8,8-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 3-methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one, spiro[4.5]decan-8-one, 7,7,9-trimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one and 8-pentyl-1-oxa-4-thiaspiro[4.5]decan-2-one.

[0023] The presence of asymmetry centers in the structure of compounds of formula (I) according to the invention results in the existence, for each of them, of several enantiomeric and / or diastereomeric forms. The invention also covers compounds represented by the general formula (I) as mixtures of enantiomers and / or diastereomers in varying proportions, in particular racemic mixtures. The invention also includes compounds of formula (I) as a single enantiomer and / or diastereomer. Mixtures of enantiomers / diastereomers or pure forms can be obtained by synthesis from optically enriched or optically pure starting materials, or by means of separation methods such as crystallization or chromatography.

[0024] A second object of the present invention relates to a composition comprising at least one compound of general formula (I) in which: R1, R2, R3, R4, R6 and R7, independently represent a hydrogen atom or a methyl group; R5 represents a hydrogen atom or a saturated linear C1-C5 alkyl group; R4 and R5 can together form a cyclopentyl group; the total number of carbon atoms being strictly greater than 9.

[0025] Preferably, a composition according to the present invention comprises at least one compound selected from 7,7-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-ethyl-3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8,8-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 3-methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one, spiro[4.5]decan-8-one oxathiolanone, 7,7,9-trimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one and 8-pentyl-1-oxa-4-thiaspiro[4.5]decan-2-one.

[0026] The effective amount of the compounds of the invention to be incorporated into these compositions depends on the nature of said compositions, the desired odor or flavoring effect, and the nature of any other odor or flavoring compounds that may be present. It is readily determined by those skilled in the art and can vary over a very wide range, from 0.000001 to 50%, in particular from 0.000005 to 20%. The preceding percentages are expressed as a percentage of the total weight of the composition.

[0027] In a first particular embodiment, the composition according to the invention is a perfume composition comprising at least one compound of general formula (I) and at least one other fragrant substance. The other fragrant 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 carbon-cyclic compounds. Such fragrant substances are mentioned, for example, in S. Arctander, "Perfume and Flavor Chemicals" (Montclair, NJ, 1969), or in "Common Fragrance and Flavor Materials," Wiley-VCH, Weinheim, 2006.Finally, several compounds of the present invention can also be used in combination in the same composition.

[0028] Due to their pleasant odor, the compounds of the invention have numerous applications in perfumery. The term "perfumery" is used here in its general sense; it refers not only to traditional perfumery (alcoholic or non-alcoholic), but also to other fields in which the scent of products is important.This may include perfumery compositions in the usual and traditional sense (such as perfume bases and concentrates, perfumes, colognes, toilet waters, air fresheners, room fragrances, scented candles and similar products), topical compositions, particularly cosmetics (such as face and / or body creams, talc 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, particularly household products (such as detergents, laundry detergents, fabric softeners, air fresheners, room fragrances and similar products).

[0029] The invention thus extends to a perfume composition comprising at least one compound of the invention. This may in particular be a composition of traditional perfumery, a cosmetic composition, a cleaning product, or even an "intermediate composition", intended to be used for the preparation of compositions or finished products (in particular perfumes, cosmetic products, cleaning products).

[0030] Such a perfumed composition is generally prepared from a base product, into which the compound(s) of the invention are incorporated. The base product will be readily determined by those skilled in the art, based on the intended composition and therefore the intended use. The composition of these base products and the nature of their usual components, such as solvent(s) and / or additive(s), are well known to those skilled in the art.

[0031] The compounds used in these perfumed compositions, in particular the compounds of the invention, can be incorporated into or onto an inert carrier material. The carrier materials that can be used are numerous and varied, for example polar solvents, oils, fats, finely divided solids, cyclodextrins, maltodextrins, gums, resins and any other carrier material known for such compositions (for example, soaps, candles, ointments, textiles, wipes, perfumed gels...).

[0032] According to another particular embodiment, the composition according to the invention is an aromatic composition comprising at least one compound of formula (I) and at least one other aromatic substance.

[0033] More specifically, an aroma composition is an ingestible product, which refers to a "foodstuff," an "edible composition," and / or a "food product." Aroma compositions may also be intended for use in tobacco. This term "ingestible product" primarily, but not exclusively, refers to products intended for human consumption, animal feed (pet food), or pharmaceutical compositions. Examples of products intended for human consumption may include, but are not limited to, snacks, confectionery, plant-based materials, and meals that may or may not provide essential nutrients. Plant-based materials include cocoa, cocoa beans, coffee, coffee beans, and tea leaves or powder.Non-limiting examples of food products include salad dressings, sauces, marinades, sticks, nutrition bars, pastries, breads, caramel, cooked cereals, meat products, poultry products, meat, poultry, fish, marine protein sources, beans, pasta, confectionery products, savory snacks, dairy products, cheeses, yogurts, 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 non-alcoholic beverages and dry powdered beverages. Non-limiting examples of beverages include soft drinks, brewed beverages, dairy products, drinkable yogurt, milk, coffee whitening agents, and nutritional drinks.Non-limiting examples of animal feed may include: pet food, especially dog ​​and cat food; rodent food; livestock feed; cattle feed; horse feed; and the like.

[0034] A third object of the present invention relates to a method for preparing compounds of formula (I) as defined above.

[0035] This process is advantageous because it is carried out in a single step and allows the use of readily available raw materials. The yield of this process is also advantageous because it is very high (nearly 80%).

[0036] The compounds of the present invention are obtained by a cyclization reaction between a cycloalkanone of formula (II) and a thiol acid of formula (III) in the presence of an acid: in which: R1, R2, R3, R4, R6 and R7, independently represent a hydrogen atom or a methyl group; R5 represents a hydrogen atom or a saturated linear C1-C5 alkyl group; R4 and R5 can together form a cyclopentyl group; the total number of carbon atoms being strictly greater than 9.

[0037] In a first embodiment, the thiolacid is thioglycolic acid.

[0038] In a second embodiment, thiolacide is thiolactic acid.

[0039] Preferably, the acid used is acid para -toluenesulfonic acid. Even more preferentially, between 1 and 5 mol% of para-toluenesulfonic acid is used relative to the reactants. The reaction is carried out under reflux at approximately 70°C in cyclohexane.

[0040] Finally, the invention has as its last object the use of at least one compound of formula (I) according to the invention in the form of a stereoisomer or a mixture of stereoisomers, or a racemic mixture to confer, modify or enhance the organoleptic properties of a substance, a composition or an article.

[0041] Organoleptic properties are defined as any property that may modify, improve or enhance the organoleptic perception of a substance, composition or article by a user.

[0042] In a first embodiment, at least one compound of formula (I) is used as a fragrance agent, alone or in combination with at least one other fragrance substance, and / or at least one solvent, and / or at least one adjuvant. The additional fragrance agent(s), solvent(s), and adjuvant(s) are known to those skilled in the art, who will be able to choose the most appropriate one(s) according to the desired effect.

[0043] The term "fragrant" is used here to refer to any organoleptic compound that pleasantly stimulates the sense of smell.

[0044] The compounds according to the invention can particularly be used as masking agents or odor neutralizers. The terms "masking agent" and "odor neutralizer" refer to reducing or eliminating the perception of an unpleasant odor generated by one or more molecules in the composition of a product.

[0045] In a second embodiment, at least one compound of general formula (I) is used as an aromatic compound, alone or in combination with at least one other aromatic substance and / or at least one solvent, and / or at least one adjuvant.

[0046] The additional flavoring agent(s), solvent(s), and adjuvant(s) are known to those skilled in the art, who will be able to choose the most suitable one(s) depending on the desired effect. The solvents used not only allow for precise dosing of the compound according to the invention for food and beverages, but also facilitate 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, for example, palm oil, soybean oil, rapeseed oil, sunflower oil, peanut oil, and medium-chain triglycerides (MCTs). Medium-chain triglycerides are triglycerides based on aliphatic fatty acids comprising 6 to 12 carbon atoms.

[0047] Aromatic means any use of the compounds of the invention for the flavoring of any liquid or solid food product, human or animal, including beverages, dairy products, ice cream, but also in tobacco flavoring applications.

[0048] In particular, the compounds according to the invention can be used alone or in combination with taste-modulating compounds, that is, compounds that modify taste and sensory perceptions. In all cases, the defining characteristic of such taste-modulating compounds is that they have no perceptible taste or aromatic properties (tasteless and aromaless). Such aroma-modifying compounds can be of synthetic or natural origin.

[0049] The following examples illustrate a particular method of preparing the compounds of the invention, as well as the olfactory / aromatic profile of each of the exemplified compounds. These examples are given for illustrative purposes only and should not be construed as limiting the general scope of the invention. Example 1: Preparation of 7,7-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one

[0050] 3,3-Dimethylcyclohexanone (the preparation of which is disclosed, for example, in application WO 2010043522) is placed in 1.1 equivalents of thioglycolic acid and 4 volumes of cyclohexane. At room temperature, 0.05 equivalents of para-toluenesulfonic acid are added. The reaction mixture is refluxed while the water formed is removed by azeotropic distillation. When the reaction is complete, the reaction mixture is poured onto a saturated aqueous solution of sodium bicarbonate. The organic phase is washed with water until the pH is neutral. After drying over magnesium sulfate, filtration, and concentration, the crude product is distilled under reduced pressure: its boiling point is 89 °C at 0.26 torr. Olfactory description: fruity, peach effect, raspberry.

[0051] The 7,7-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained exhibits the following spectral characteristics: 1< H-RMN(300 MHz, CDCl 3): δ (ppm) 3.73 (s, 1H), 3.72 (s, 1H), 2.10 - 1.90 (m, 2H), 1.85 - 1.58 (m, 4H), 1.46 - 1.29 (m, 1H), 1.34 - 1.16 (m, 1H), 1.04 (s, 3H), 0.97 (s, 3H). 13< C-RMN (75 MHz, CDCl 3): δ (ppm) 172.34, 92.16, 51.31, 39.82, 37.74, 32.23, 31.11, 28.37, 19.90. SM [EI +< ] ( m / z ) (%): 200 (M+, 9), 127(100), 109(55), 83(25), 69(34), 56(10), 55(35), 46(12), 43(26), 41(25), 39(10). IR (pure, cm -1<): 2946m, 1765s, 1455w, 1215m, 1144m, 1060m, 1025m, 993m, 954m, 914w, 811w, 797w, 607w. Example 2: Preparation of 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one

[0052] 8-Ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described in Example 1 using 4-ethylcyclohexanone instead of 3,3-dimethylcyclohexanone. The crude product, obtained as two diastereomers in a 54:46 ratio, is distilled under reduced pressure: its boiling point is 98 °C at 0.18 torr. Olfactory description: exotic fruits, mango, guava, papaya.

[0053] The 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained exhibits the following spectral characteristics: Major isomer (54%): 1< H-RMN (300 MHz, CDCl 3): δ (ppm) 3.62 (s, 2H), 2.21-2.06 (m, 1H), 2.05-1.88 (m, 2H), 1.80-1.60 (m, 3H), 1.40-1.23 (m, 1H), 1.26-1.04 (m, 4H), 0.81 (td, J = 7.2 Hz, 3H). 13< C-RMN (75 MHz, CDCl 3): δ (ppm) 172.24, 94.34, 38.70, 37.43, 31.69, 39.34, 11.57. SM [EI +< ] ( m / z ) (%): 200 (M+, 10), 127 (100), 109 (37), 67 (33), 55 (41), 46 (12), 43 (13), 41 (22). Minor isomer (46%): 1< H-RMN (300 MHz, CDCl 3): δ (ppm) 3.69 (s, 2H), 2.21-2.06 (m, 1H), 2.05-1.88 (m, 2H), 1.80-1.60 (m, 3H), 1.40-1.23 (m, 1H), 1.26-1.04 (m, 4H), 0.81 (td, J = 7.2 Hz, 3H). 13< C-RMN (75 MHz, CDCl 3): δ (ppm) 172.26, 91.48, 39.49, 37.17, 32.25, 29.12, 28.69, 11.47. SM [e / m (%)]: 200 (M+, 10), 129(10), 127 (100), 109 (35), 67 (33), 55(42), 46(12), 43 (14), 41 (23). IR (pure, cm -1<): 2926m, 1767s, 1442w, 1197m, 1139m, 1041m, 966m, 915w, 892w, 854w, 796w. Example 3: Preparation of 8-ethyl-3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one

[0054] 8-Ethyl-3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described in Example 1, using 4-ethylcyclohexanone instead of 3,3-dimethylcyclohexanone, thiolactic acid (1.3 equivalents) instead of thioglycolic acid, and toluene instead of cyclohexane. The crude product, obtained as two diastereomers in a 42:58 ratio, is distilled under reduced pressure; its boiling point is 88 °C at 0.4 mbar. Olfactory description: peach, green, tomato leaf.

[0055] The 8-ethyl-3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained exhibits the following spectral characteristics: Major isomer (58%): 1< H-RMN (300 MHz, CDCl 3): δ (ppm) 3.99 (q, J = 7.0 Hz, 1H), 2.28 - 2.09 (m, 1H), 2.09 - 1.61 (m, 5H), 1.57 (d, J= 7,0 Hz, 3H), 1,52 - 0,95 (m, 5H), 0,88 (t, J = 7,0 Hz, 3H). 13< C-RMN (75 MHz, CDCl 3 ): δ (ppm) 175,19, 91,63, 40,90, 39,61, 38,96, 37,52, 29,78, 29,15, 28,71, 18,40, 11,60. SM [EI +< ] ( m / z ) (%): 210 (M+, 0,3), 195 (100), 137 (24), 109 (34), 101 (998), 93 (10), 91 (14), 81 (11), 79 (15), 76 (15), 67 (16), 43 (64), 41 (16). Isomère minoritaire (42%) : 1< H-RMN (300 MHz, CDCl 3 ): δ (ppm) 3,99 (q, J = 7,0 Hz, 1H), 2,28 - 2,09 (m, 1H), 2,09 - 1,61 (m, 5H), 1,58 (d, J = 7,0 Hz, 3H), 1,52 - 0,95 (m, 5H), 0,87 (t, J = 7,0 Hz, 3H). 13< C-RMN (75 MHz, CDCl 3 ): δ (ppm) 175,25, 88,74, 41,43, 40,27, 39,74, 37,28, 29,23, 29,06, 28,76, 18,54, 11,50. SM [EI +< ] ( m / z ) (%): 214 [M +< ] (6), 127 (100), 109 (19), 67 (12), 60 (20), 55 (23), 41 (15). IR (film, cm -1< ): 1039m, 1209m, 1447s, 1761s, 2928m. Example 4: Preparation of 8,8-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one

[0056] 8,8-Dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described in Example 1 using 4,4-dimethylcyclohexanone instead of 3,3-dimethylcyclohexanone. The crude product is distilled under reduced pressure: its boiling point is 92 °C at 0.39 torr. Olfactory description: fruity, green, exotic fruits.

[0057] The 8,8-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained exhibits the following spectral characteristics: 1< H-RMN (300 MHz, CDCl 3): δ (ppm) 3.71 (s, 2H), 2.19-2.01 (m, 2H), 1.98-1.80 (m, 2H), 1.63-1.30 (m, 4H), 0.94 (2s, 6H). 13< C-RMN (75 MHz, CDCl 3): δ (ppm) 172.35, 93.19, 36.05, 35.74, 31.95, 29.11. SM [EI +< ] ( m / z ) (%): 200 (M+, 12), 127(100), 109 (35), 71(15), 67 (16), 55(33), 46 (15), 43(24), 41 (24), 39(10). IR (pure, cm -1<): 2950m, 1767s, 1444w, 1232m, 1215m, 1156m, 1045s, 1001m, 972m, 877m, 791w, 585w. Example 5 : Preparation of 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one

[0058] 8-Propyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described in Example 1 using 4-propylcyclohexanone instead of 3,3-dimethylcyclohexanone. The crude product, obtained as two diastereomers in a 46:54 ratio, is distilled under reduced pressure: its boiling point is 106-110 °C at 0.2 torr. Olfactory description: peach, apricot, juicy, pulpy.

[0059] The 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained exhibits the following spectral characteristics: Major isomer (54%): 1< H-RMN (300 MHz, CDCl 3): δ (ppm) 3.74 (s, 2H), 2.22-2.16 (m, 1H), 2.05-1.95 (m, 2H), 1.85-1.64 (m, 3H), 1.40-1.11 (m, 7H), 0.89-0.84 (t, J = 7.2 Hz, 3H). 13< C-RMN (75 MHz, CDCl 3): δ (ppm) 172.38, 94.50, 38.79, 38.27, 31.78, 29.73, 20.12, 14.27. SM [EI +< ] ( m / z) (%): 214 (M+, 7), 142(10), 141(100), 81(43), 67(20), 55(28), 46(10), 43(10), 41(18). Isomère minoritaire (46%) : 1< H-RMN (300 MHz, CDCl 3 ): δ (ppm) 3,68 (s, 2H), 2,22-2,16 (m, 1H), 2,05-1,95 (m, 2H), 1,85-1,64 (m, 3H), 1,40-1,11 (m, 7H), 0,89-0,84 (t, J = 7,2 Hz, 3H). 13< C-RMN (75 MHz, CDCl 3 ): δ (ppm) 172,38, 91,65, 39,58, 38,24, 32,24, 29,50, 20,00, 14,27. MS [e / m (%)]: 214 (M+, 9), 141(100), 81(39), 67(19), 55(22), 41(15). IR (pur, cm -1< ): 2926m, 1768s, 1443w, 1223m, 1193m, 1137w, 1043m, 969m, 912w, 842w, 796w, 589w. Example 6: Preparation of 3-methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one

[0060] 3-Methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described in Example 1, using 4-propylcyclohexanone instead of 3,3-dimethylcyclohexanone, thiolactic acid (1.3 equivalents) instead of thioglycolic acid, and toluene instead of cyclohexane. The crude product, obtained as two diastereomers in a 44:56 ratio, is distilled under reduced pressure; its boiling point is 95 °C at 0.4 mbar. Olfactory description: peach, fruity, green.

[0061] The 3-methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained exhibits the following spectral characteristics: Major isomer (56%): 1< H-RMN (300 MHz, CDCl 3): δ (ppm) 3.98 (q, J = 7.0 Hz, 1H), 2.26 - 1.61 (m, 6H), 1.56 (d, J = 7.0 Hz, 3H), 1.51 - 0.95 (m, 7H), 0.87 (t, J = 7.0 Hz, 3H). 13< C-RMN(75 MHz, CDCl 3 ): δ (ppm) 175,12, 91,56, 41,39, 40,86, 39,60, 38,95, 38,25, 35,48, 30,12, 20,11, 18,38, 14,26. SM [EI +< ] ( m / z ) (%): 228 [M +< ] (3), 142 (10), 141 (100), 81 (20), 67 (10) Isomère minoritaire (44%) : 1< H-RMN (300 MHz, CDCl 3 ): δ (ppm) 4,06 (q, J = 7,0 Hz, 1H), 2,26 - 1,61 (m, 6H), 1,57 (d, J = 7,0 Hz, 3H), 1,51 - 0,95 (m, 7H), 0,86 (t, J = 7,0 Hz, 3H). 13< C-RMN (75 MHz, CDCl 3 ): δ (ppm) 175,18, 88,68, 41,39, 40,24, 39,73, 38,30, 35,22, 29,56, 29,40, 19,99, 18,52, 14,26. SM [EI +< ] ( m / z ) (%): 228 [M +< ] (3), 142 (10), 141 (100), 81 (20), 67 (10), 60 (13) IR (film, cm -1< ): 1036m, 1224m, 1443m, 1755s, 1926m. Example 7: Preparation of oxathiolanone from spiro[4.5]decan-8-one

[0062] The oxathiolanone from spiro[4.5]decan-8-one is prepared according to the protocol described in Example 1, using spiro[4.5]decan-8-one instead of 3,3-dimethylcyclohexanone. The crude product is recrystallized from cyclohexane. Olfactory description: peach, velvety, green, vanilla effect.

[0063] The oxathiolanone from the spiro[4.5]decan-8-one thus obtained exhibits the following spectral characteristics: 1< H-RMN (300 MHz, CDCl 3): (ppm) 3.74 (s, 2H), 2.16-2.07 (m, 2H), 1.97-1.88 (m, 2H), 1.69-1.59 (m, 6H), 1.54-1.43 (m, 6H). 13< C-RMN (75 MHz, CDCl 3): δ (ppm) 172.42, 93.38, 41.20, 37.02, 34.68, 32.00, 24.45, 24.39. SM [EI +< ] ( m / z ) (%): 226 (M+, 6), 154(11), 153(100), 135(10), 67(14), 55(15). IR (pure, cm -1<): 2943m, 1771s, 1443m, 1267m, 1221s, 1209s, 1131m, 1041s, 978m, 933m, 900w, 838m, 794m, 608w. Example 8: Preparation of 7,7,9-trimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one

[0064] 7,7,9-Trimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described in Example 1 using 3,5,5-trimethylcyclohexanone instead of 3,3-dimethylcyclohexanone. The crude product, obtained as two diastereomers in a 74:26 ratio, is distilled under reduced pressure: its boiling point is 87 °C at 0.04 torr. Olfactory description: peach, woody, camphor, green.

[0065] The 7,7,9-trimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained exhibits the following spectral characteristics: Major isomer (74%): 1< H-RMN (300 MHz, CDCl 3): δ (ppm) 3.73 (s, 2H), 2.19-2.06 (m, 1H), 2.04-1.84 (m, 2H), 1.57-1.25 (m, 3H), 1.06 (s, 3H), 0.97-0.80 (m, 7H). 13< C-RMN (75 MHz, CDCl 3): δ (ppm) 172.53, 91.83, 51.48, 48.37, 46.93, 33.48, 32.74, 32.18, 26.67, 25.98, 21.89. SM [EI +< ] ( m / z) (%): 214 (M+, 7), 142(10), 141(100), 123(14), 83(85), 69(15), 55(25), 46(10), 43(11), 41(22). Isomère minoritaire (26%) : 1< H-RMN (300 MHz, CDCl 3 ): δ (ppm) 3,65 (s, 2H), 2,19-2,06 (m, 1H), 2,04-1,84 (m, 2H), 1,57-1,25 (m, 3H), 1,04 (s, 3H), 0,97-0,80 (m, 7H). 13< C-RMN (75 MHz, CDCl 3 ): δ (ppm) 171,99, 93,57, 49,67, 47,62, 47,15, 33,56, 32,46, 32,29, 26,59, 26,38, 21,64. SM [EI +< ] ( m / z ) (%): 214 (M+, 5), 142(11), 141(100), 123(16), 83(88), 69(16), 55(25), 46(10), 43(13), 41(24), 39(10). IR (pur, cm -1< ): 2951m, 1766s, 1456w, 1210m, 1167m, 1139w, 1022m, 1005m, 958m, 896w, 859w, 798w, 612w. Example 9: Preparation of 8-pentyl-1-oxa-4-thiaspiro[4.5]decan-2-one

[0066] 8-Pentyl-1-oxa-4-thiaspiro[4.5]decan-2-one is prepared according to the protocol described in Example 1 using 4-pentylcyclohexanone instead of 3,3-dimethylcyclohexanone. The crude product, obtained as two diastereomers in a 45:55 ratio, is distilled under reduced pressure: its boiling point is 135 °C at 0.2 torr. Olfactory description: peach, fruity, herbaceous.

[0067] The 8-pentyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained exhibits the following spectral characteristics: Major isomer (55%): 1< H-RMN (300 MHz, CDCl 3): δ (ppm) 3.67 (s, 2H), 2.21-2.14 (m, 1H), 2.06-1.90 (m, 2H), 1.84-1.64 (m, 3H), 1.40-1.11 (m, 11H), 0.88-0.83 (t, J = 7.2 Hz, 3H). 13< C-RMN (75 MHz, CDCl 3): δ (ppm) 172.32, 94.45, 38.79, 35.94, 35.76, 32.02, 31.99, 29.76, 22.60 14.06. SM [EI +< ] ( m / z) (%): 242 (M+, 4), 170(12), 169(100), 95(24), 81(24), 67(12), 55(24), 43(12), 41(23). Isomère minoritaire (45%) : 1< H-RMN (300 MHz, CDCl 3 ): δ (ppm) 3,73 (s, 2H), 2,21-2,14 (m, 1H), 2,06-1,90 (m, 2H), 1,84-1,64 (m, 3H), 1,40-1,11 (m, 11H), 0,88-0,83 (t, J = 7,2 Hz, 3H). 13< C-RMN (75 MHz, CDCl 3 ): δ (ppm) 172,32, 91,61, 39,58, 35,97, 35,49, 32,31, 31,75, 29,53, 26,58, 22,62, 14,27. SM [e / m (%)]: 242 (M+, 4), 170(12), 169(100), 95(21), 81(21), 67(12), 55(25), 43(13), 41(23). IR (pur, cm -1< ): 2922m, 2853m, 1769s, 1443w, 1209m, 1184m, 1133w, 1041m, 982m, 901w, 796w. Example 10: Perfume composition comprising the derivatives obtained in examples 2, 5 or 7 applied in a shampoo base (at a rate of 0.6%)

[0068] In a pink accord prepared according to the following table (Accord A) are added: - 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one (compound 16025-37, Example 5, Accord B) - 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one (compound 16025-43, Example 2, Accord C) - oxathiolanone of spiro[4.5]decan-8-one (compound 16025-56, Example 7, Accord D) Ingredients A B C D CITRONELLOL 300 300 300 300 GERANIOL 150 150 150 150 PHENYLETHYL ALCOHOL 150 150 150 150 PHENOXYETHYL ISOBUTYRATE 80 80 80 80 DIPHENYL OXIDE 80 80 80 80 NEROL 75 75 75 75 ISOAMYL ACETATE 10% DPG 25 25 25 25 GERANIUM ESS 20 20 20 20 ROSE OXIDE 20 20 20 20 CITRAL 15 15 15 15 OXACYCLOHEXADECAN-2-ONE 15 15 15 15 MAGNOLAN ™< 7 7 7 7 DAMASCENONE 10% DPG 7 7 7 7 FRUCTONE ™< 5 5 5 5 RASPBERRY KETONE 5 5 5 5 METHYL PHENYLETHYL ETHER 10% DPG 5 5 5 5 OXANE 50%TEC 3 3 3 3 DIMETHYL SULFIDE 3 3 3 3 VANILLIN 1 1 1 1 DIPROPYLENE GLYCOL - DPG 34 29 29 29 Compound 16025-37 - 5 - - Compound 16025-43 - - 5 - Compound 16025-56 - - - 5 1000 1000 1000 1000

[0069] Adding 5 parts of compound 16025-37 to accord A elegantly enhances the rosy-fruity effect, creating a more petal-like, natural feel. Adding compound 16025-43 in the same proportions brings a more woody, peachy character, resulting in a richer, more opulent rose. The addition of compound 16026-56 introduces a more "hard" facet, with green notes. The accord is less rosy than in the previous two cases, more fruity, with grapefruit notes, and still more intense than accord A.

[0070] In all cases, the addition of a molecule according to the invention brings power and a green note which blends well with the overall accord of the perfume composition. Example 11 : Perfume composition comprising the derivatives obtained in examples 2, 5 or 7 applied in a fabric softener base (at a rate of 1%)

[0071] In a fruity-gourmand accord created according to the following table (Accord A), the following are added: 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one (compound 16025-37, Example 5, Accord B) 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one (compound 16025-43, Example 2, Accord C) spiro[4.5]decan-8-one oxathiolanone (compound 16025-56, Example 7, Accord D) Ingredients A B C D HEXYLCINNAMIUM ALDEHYDE 125 125 125 125 METHYL DIHYDRO JASMONATE 80 80 80 80 ETHYL VANILLIN 75 75 75 75 ISO E 45 45 45 45 HEXYL SALICYLATE 45 45 45 45 4 tBu CYCLOHEXYL ACETATE 40 40 40 40 HABANOLIDE 40 40 40 40 VANILLIN 38 38 38 38 VERDYL ACETATE 35 35 35 35 2 tBu CYCLOHEXYL ACETATE 50% DPG 30 30 30 30 ROSAFIX 25 25 25 25 TETRAHYDROLINALOL 25 25 25 25 Anisic Aldehyde 25 25 25 25 FLOROL ™< 25 25 25 25 PHENOXYETHYL ISOBUTYRATE 25 25 25 25 ORANGE TERPENES 25 25 25 25 GERANIOL 23 23 23 23 GAMMA UNDECALACTONE 23 23 23 23 PHENYLETHYL ALCOHOL 18 18 18 18 ETHYL METHYL PHENYL GLYCIDATE 17 17 17 17 GAMMA NONALACTONE 17 17 17 17 ETHYL MALTOL 14 14 14 14 SILVIAL™ < 10% DPG 14 14 14 14 ALPHA ISOMETHYL IONONE 12 12 12 12 GERANYL ACETATE 10% DPG 12 12 12 12 LINALYL ACETATE 10 10 10 10 1-(2,3-DIMETHYL-BICYCLO[2.2.1]HEPT-2-YL)-ETHANONE 1% DPG 9 9 9 9 COUMARIN 7 7 7 7 CIS-3-HEXENYL SALICYLATE 7 7 7 7 BENZYL ACETATE 6 6 6 6 METHYL ANTHRANILATE 6 6 6 6 FRAMBINONE 6 6 6 6 DMBC BUTYRATE 6 6 6 6 ETHYL CINNAMATE 6 6 6 6 MADERAL ™< 5 5 5 5 DAMASCENONE 10% DPG 5 5 5 5 LIFFAROME™ < 10% DPG 5 5 5 5 ETHYL METHYLVALERATE 10% DPG 4 4 4 4 DELTA DAMASCONE 4 4 4 4 HELIOTROPINE 4 4 4 4 CYCLOGALBANATE™ < 10% DPG 4 4 4 4 PATCHOULY EO 2 2 2 2 6-[2,4,4-TRIMETHYL-CYCLOPENTYLIDENE]-HEXANAL 1% DPG 2 2 2 2 ORCANOX ™< 2 2 2 2 Compound 16025-37 - 3 - - Compound 16025-43 - - 3 - Compound 16025-56 - - - 3 DIPROPYLENE GLYCOL - DPG 50 47 47 47 1000 1000 1000 1000

[0072] Adding 3 parts of compound 16025-37 to accord A brings a lot of power and gives a more vibrant green note, while adding compound 16025-43 rounds out the note even more, with a more present and powerful gourmand, vanilla effect.

[0073] The addition of compound 16025-56 also rounds out the accord, while compressing the fruity notes at this dosage. Example 12: Aromatic composition including the derivative obtained in example 5 applied in a yogurt (at a level of 0.08% or 160ppb)

[0074] Ingredients A B Acetyl Methyl Carbinol 50% PG 2 2 STRAWBERRY FURANONE 30% PG 3 3 PROPIONIC ACID 12,5 12,5 BUTYRIC ACID 15 15 BUTYL ALCOHOL 15,5 15,5 GAMMA DECALACTONE 17,5 17,5 ACETIC ACID (CO2) 20 20 ETHYL ACETATE 20 20 LINALOOL 25 25 CO5 BUTYRIC ACID METHYL 2 25 25 APRICOT BPL 48,5 48,5 PROPYLENE GLYCOL 796 794,5 Compound 16025-37 10% PG - 2 1000 1000

[0075] Adding compound 16025-37 at 160 ppb to the yogurt gives the peach flavor a more authentic, rounder, peach nectar profile. Example 13 : Aromatic composition including the derivative obtained in example 5 applied in a yogurt (at a level of 0.02% or 140ppb)

[0076] Ingredients A B BUTYRIC ACID 15 15 GAMMA DECALACTONE 7 7 ACETIC ACID (CO2) 12 12 LINALOOL 1,5 1,5 CO5 BUTYRIC ACID METHYL 2 6 6 THIAZOLE ISOPROPYL METHYL 1% ALC 1 1 BUCHU DETERPENE ESSENCE 1% ALC 1,4 1,4 GERANYL ACETATE 1,5 1,5 GAMMA HEXALACTONE S 2,5 2,5 HEXYL ACETATE 3 3 BENZOIC ALDEHYDE 3 3 DELTA DECALACTONE 3 3 MALTOL 3 3 GAMMA DODECALACTONE S 3,5 3,5 HEXENOL CIS 3 4,5 4,5 HEXENYL CIS 3 ACETATE 9 9 LIMONENE 9 9 ISOAMYL ACETATE 15 15 ETHYL ALCOHOL CO2 899,1 897,1 Compound 16025-37 10%PG 7 1000 1000

[0077] The addition of compound 16025-37 at a concentration of 140 ppb complicates the apricot profile, imparting a very natural, apricot flesh, juice-like quality—very good. The profile of this apricot aroma is very distinctive and could not be reproduced using other prior art compounds. Example 14: Olfactometry Tests

[0078] It is generally accepted that the ratio of volatility to the detection threshold of an odor yields an "odor value" (or "O2"). Gold Value "), a unitless value that represents the olfactory strength of a molecule. The higher this value, the more potent the molecule. Therefore, to calculate this Odor Value, the volatility and the detection threshold must be determined.

[0079] In the present study, two molecules of the invention are tested to determine their potency (via their Odor Value) compared to a prior art reference molecule, gamma-undecalactone. The two molecules of the invention that are tested are that of Example 2 (8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one) and that of Example 5 (8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one).

[0080] Initially, the volatility values ​​at 20°C of the molecules in example 2 and example 5 are determined by ebulliometry. These values ​​are respectively 19.8 µg.l-1 and 7.8 µg.l-1.

[0081] In a second step, psychosensory studies were carried out in order to determine the detection threshold of the two molecules according to the present invention and also that of gamma-undecalactone.

[0082] The detection threshold value was obtained using a dynamic olfactometer constructed according to the guidelines of ISO 13725 and ISO 13301. It corresponds to the critical statistical gas concentration required to elicit a positive response from a minimum of eighteen panelists aged 22 to 57 years, using a forced-choice model. One choice was a controlled dilution of an air stream saturated with the raw material, and the other was a neutral air stream. Random repetition of these choices for a set of five to eight gas concentrations allowed for the determination of the detection threshold after statistical processing of the data obtained. Thus, the detection threshold for the molecules in Example 2 and Example 5 was determined to be 0.016 ng / L and 0.075 ng / L, respectively.

[0083] Thus, after these measurements, it is possible to calculate the Odor Value of the molecules according to the invention in comparison to that of gamma-undecalactone. Odor Value = Valeur de volatilité / Seuil de détection

[0084] The Odor Value is equal to 1,222,223 for the molecule according to example 2, and to 104,133 for the molecule according to example 5. However, for gamma-undecalactone the Odor Value determined under identical experimental conditions is 5,473.

[0085] In conclusion, the Odor Value of the molecules according to the invention (of examples 2 and 5) is much clearly superior to that of gamma-undecalactone, which indicates that said molecules according to the invention are much more powerful than gamma-undecalactone.

[0086] In addition, the substantiveness assessed by the panelists is equal to 2.59 for the molecule according to example 2, and to 2.62 for the molecule according to example 5.

Claims

1. A compound of the following general formula (I): wherein: - R1, R2, R3, R4, R6 and R7, independently represent a hydrogen atom or a methyl group; - R5 represents a hydrogen atom or a saturated linear C1-C5 alkyl group; - R4 and R5 may together form a cyclopentyl group; - the total number of carbon atoms being strictly greater than 9.

2. The compound according to claim 1, characterised in that R5 represents a saturated linear C1-C5 alkyl group.

3. The compound according to claim 1 or 2 characterised in that R1, R2, R3, R4, R6 and R7, represent a hydrogen atom.

4. The compound according to any one of claims 1 to 3 characterised in that the total number of carbon atoms is 10 or 11.

5. The compound according to any one of the preceding claims, characterised in that it is selected from the 7,7-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-ethyl-3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8,8-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 3-methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one, oxathiolanone of the spiro[4.5]decan-8-one, 7,7,9-trimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one and 8-pentyl-1-oxa-4-thiaspiro[4.5]decan-2-one.

6. A composition comprising at least one compound of the following general formula (I): wherein: - R1, R2, R3, R4, R6 and R7, independently represent a hydrogen atom or a methyl group; - R5 represents a hydrogen atom or a saturated linear C1-C5 alkyl group; - R4 and R5 may together form a cyclopentyl group; - the total number of carbon atoms being strictly greater than 9.

7. The composition according to claim 6, said composition comprising at least one compound selected from the 7,7-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-ethyl-3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8,8-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one, 3-methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one, oxathiolanone of the spiro[4.5]decan-8-one, 7,7,9-trimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one and 8-pentyl-1-oxa-4-thiaspiro[4.5]decan-2-one.

8. The composition according to claim 6 or 7, characterized in that the compound of formula (I) is present in a concentration of between 0.000001 to 50% by weight with respect to the total weight of the composition, more particularly between 0.000005 to 20%.

9. The composition according to any one of claims 6 to 8 characterized in that it is a perfume composition comprising at least one compound of formula (I) and at least one other odorant.

10. The composition according to any one of claims 6 to 8 characterised in that it is an aromatic composition comprising at least one compound of formula (I) and at least one other aromatic substance.

11. A method for the preparation of a compound of formula (I) as described in claims 1 to 5 by a cyclization reaction between a cycloalkanone of formula (II) and a thiolacid of formula (III) in the presence of an acid wherein: - R1, R2, R3, R4, R6 and R7, independently represent a hydrogen atom or a methyl group; - R5 represents a hydrogen atom or a saturated linear C1-C5 alkyl group; - R4 and R5 may together form a cyclopentyl group; - the total number of carbon atoms being strictly greater than 9.

12. The method according to claim 11, characterised in that the thiolacid is thioglycolic acid.

13. The method according to claim 11 characterised in that the thiolacid is thiolactic acid.

14. The method according to any one of claims 11 to 13 characterised in that the acid used is para-toluene sulphonic acid.

15. Use of at least one compound of general formula (I) as defined in claims 1 to 5 in the form of a stereoisomer or a mixture of stereoisomers, or a racemic mixture for conferring, modifying or enhancing the organoleptic properties of a substance, composition or article.

16. Use according to claim 15 of at least one compound of formula (I) as a fragrance agent, alone or in combination with at least one other odorant, and / or at least one solvent, and / or at least one adjuvant.

17. Use according to claim 15 of at least one compound of the general formula (I) as an aromatic compound, alone or in combination with at least one other aromatic substance and / or at least one solvent, and / or at least one adjuvant.