RU2796534C2 - New spirooxathiolanone compounds, method of their production and their application in perfume and aromatic compounds - Google Patents

Abstract

FIELD: pharmaceuticals.

SUBSTANCE: invention relates to compounds of general formula (I), which can be used to impart, change or enhance the organoleptic properties of a substance, composition or product. In formula (I), 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 is strictly greater than 9.

EFFECT: invention also relates to a composition containing these compounds, a method for their preparation and use for imparting, changing or enhancing the organoleptic properties of a substance, composition or product.

17 cl, 4 tbl, 14 ex

Description

The present invention is directed to new compounds of the spirooxathiolanone type having fruity, peach and/or exotic fruit notes, a method for their preparation, as well as their use in the chemical industry, in particular in perfumery, cosmetics, parapharmacy, in the production of detergents, as well as in the food industry. industry, these compounds have suitable organoleptic properties, as well as a certain intensity and durability.

In order to expand the range of notes that perfumers and fragrance creators can use to complement their developments, the perfume industry and the fragrance industry are constantly searching for new organoleptic compounds, both to meet increasing regulatory requirements, and in terms of replacing compounds recognized as unacceptable by legislative bodies. , and even invalid ones. In addition, cost limits are becoming more and more stringent.

There are very few compounds with fruity, peach and/or exotic fruit notes among the sensation-defined molecules. The most commonly used compounds are gamma-undecalactone, Nectaryl ^® (Givaudan) or Apritone ^® (Bedoukian):

However, prior art compounds, and in particular the above compounds, have fruity, peach and/or exotic fruity notes, always accompanied by an oily, lactonic, creamy component that imparts an unnatural flavor or fragrance that is not preferred.

In addition, in order to meet the continuing needs of the perfume and fragrance industries and to broaden the palette for perfumers and fragrance makers, Applicant has identified new spirooxathiolanone compounds providing an original fruity, peach and/or exotic fruity note with the advantage of giving compositions a natural appearance. These compounds have sufficiently intense notes that they can be used at very low final concentrations in ready-to-eat scent and flavor compositions.

These spirooxathiolanone compounds correspond to the following formula (I):

Where:

R ₁ , R ₂ , R ₃ , R ₄ , R ₆ and R ₇ independently represent a hydrogen atom or a methyl group;

R ₅ represents a hydrogen atom or a saturated linear C ₁ -C ₅ alkyl group;

R ₄ and R ₅ may together form a cyclopentyl group;

the total number of carbon atoms is strictly greater than 9.

The present invention also relates to a composition containing at least one compound of general formula (I).

In addition, the third object of the present invention relates to a process for the preparation of a compound of general formula (I), said process being simple, preferable in terms of yield, including one single step, and therefore economical.

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

To the best of the applicant's knowledge, none of the compounds corresponding to the general formula (I) has been identified so far.

Spirolactone compounds useful in perfumery have been identified in the prior art, such as in US Pat. No. 4,519,944, which discloses compounds of the following formula:

These compounds differ not only structurally from the compounds of the present invention, but they have (for the preferred compounds) woody, milky, lactonic, powdery notes, respectively, which are indeed different from those of the compounds described in the present invention.

Moreover, scientific publications reveal some spirooxathiolanone compounds, but without specifying their organoleptic properties. For example, 7-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one and 3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one are given (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).

Finally, Japanese patent application JP 2001039972 (Hasegawa) describes oxathiolanones having a meaty, nutty, cooking odor, with the general formula:

and, therefore, in essence, not at all fruity, peach and/or exotic notes of the compounds described in the present invention.

The spirooxathiolanone compounds of the present invention have, on the one hand, a chemical structure that is essentially new and different from that of the compounds of the prior art, and on the other hand, fruity, peach and/or exotic fruity notes, giving a natural appearance to the compositions, and relative to control compounds. In addition, the compounds of the invention have very low odor detection thresholds, in particular compared to the reference compound, which is gamma-undecalactone. However, compared to gamma-undecalactone, the spirooxathiolanone compounds of the present invention have an "odor number" derived from the volatility/odor detection threshold) much greater than that of gamma-undecalactone, thus demonstrating the intensity of these compounds in relation to the intensity of gamma-undecalactone.

Thus, the present invention relates to spirooxathiolanone compounds of the following general formula (I):

Where:

R ₁ , R ₂ , R ₃ , R ₄ , R ₆ and R ₇ independently represent a hydrogen atom or a methyl group;

R ₅ represents a hydrogen atom or a saturated linear C ₁ -C ₅ alkyl group;

R ₄ and R ₅ may together form a cyclopentyl group;

the total number of carbon atoms is strictly greater than 9.

Within the meaning of the present invention, the term "C ₁ -C ₅ -alkyl" means any monovalent radical derived from a saturated linear carbonized chain containing 1 or 5 carbon atoms, that is, a methyl, ethyl, propyl, butyl and pentyl group.

According to the first embodiment, R ₅ is a saturated linear C ₁ -C ₅ alkyl group. Preferably R ₅ is an ethyl or propyl group.

According to another preferred embodiment, R ₁ , R ₂ , R ₃ , R ₄ , R ₆ and R ₇ represent a hydrogen atom.

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

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

In a preferred embodiment, the compound of 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- she, 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, spirooxathiolanone[4.5]decan-8- she, 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.

The presence of asymmetric centers in the structure of the compounds of formula (I) according to the invention causes the existence for each of them of several enantiomeric and/or diastereomeric forms. The invention also relates to compounds represented by the general formula (I) in the form of enantiomeric and/or diastereomeric mixtures in various proportions, in particular racemic mixtures. The invention also includes compounds of formula (I) in the form of one single enantiomer and/or diastereomer. Enantiomeric/diastereomeric mixtures or pure forms can be obtained by synthesis from starting materials that are optically enriched or optically pure, or by crystallization or chromatography separation techniques.

The second object of the present invention relates to a composition containing at least one compound of general formula (I)

Where:

R ₁ , R ₂ , R ₃ , R ₄ , R ₆ and R ₇ independently represent a hydrogen atom or a methyl group;

R ₅ represents a hydrogen atom or a saturated linear C ₁ -C ₅ alkyl group;

R ₄ and R ₅ may together form a cyclopentyl group;

the total number of carbon atoms is strictly greater than 9.

Preferably the composition of the present invention contains 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, spirooxathiolanone[ 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- she.

The effective amount of the compounds of the present invention to be included in these compositions depends on the properties of said compositions, the desired odorant or fragrance effect, and the properties of other odorant or fragrance compounds that may be present. It is easily determined by a person 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 previous percentages are expressed by the total weight of the composition.

In a first specific embodiment, the composition according to the invention is a perfume composition containing at least one compound of general formula (I) and at least one other odorant. Other odorants 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 and the like, as well as synthetic products such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, esters, acetals, nitriles and the like, in particular saturated or unsaturated, aliphatic, heterocyclic or carbocyclic compounds. Such odorants are listed, for example, in S. Arctander, "Perfume and Flavor Chemicals" (Montclair, N.J., 1969), or also in "Common Fragrance and Flavor Materials", Wiley-VCH, Weinheim, 2006. Finally, several compounds according to the present invention can also be used in combination in the same composition.

Due to the pleasant odor they give off, the compounds of the present invention have many uses in perfumery. The term "perfume" is used here in a general sense; it denotes not only traditional perfume production (alcohol or not), but also other areas in which the smell of products is important. Thus, reference can be made to perfume compositions in the conventional and traditional sense (such as perfume bases and concentrates, perfumes, colognes, eau de toilette, air fresheners, room fragrances, scented candles and similar products), to topical applications, in particular to cosmetics. compositions (such as face and/or body creams, talcum powders, hair oils, shampoos, hair lotions, bath salts and oils, shower and/or bath gels, bath soaps, antiperspirants and body deodorants, lotions and shaving creams, soaps, toothpastes, mouthwashes, balms and similar products), as well as care products, in particular home care products (such as detergents, washing powders, softeners, air fresheners, fragrances indoor and similar products).

The invention thus extends to a perfume composition containing at least one compound of the invention. In particular, it may refer to a traditional perfume composition, a cosmetic composition, a care product or also a "so-called intermediate composition" intended to be used for the preparation of final compositions or final products (in particular perfumes, cosmetics, care products) .

Such a perfume composition is usually obtained from the main product, which includes the compound(s) according to the invention. The main product is easily determined by a person skilled in the art depending on the intended composition and, therefore, on the intended use. The composition of these base products and the properties of their common components such as solvent(s) and/or additive(s) are well known to the person skilled in the art.

The compounds included in these perfume compositions, in particular the compounds of the invention, may be incorporated into or on an inert carrier material. Carrier materials that can be used are many and varied, e.g. polar solvents, oils, fats, finely divided solids, cyclodextrins, maltodextrins, gums, resins and any other carrier material known for such compositions (e.g. soaps, suppositories, balms , textiles, napkins, perfumed gels, etc.).

According to another specific embodiment, the composition of the invention is an aromatic composition containing at least one compound of formula (I) and at least one other aromatic substance.

More specifically, the aroma composition is an ingestible product that refers to a "food", "edible composition" and/or "food product". The aromatic composition may also be intended for use in tobacco. Said oral product preferably refers, without limitation, to products intended for human nutrition, for animal (pet) nutrition or also for pharmaceutical compositions. Examples of products intended for human nutrition may include, but are not limited to, snacks, sweets, vegetable matter, and meals that may (or may not) provide essential nutrients. Plant matter includes cocoa, cocoa beans, coffee, coffee beans, and tea leaves or powder. Non-limiting examples of food products include vinegared dressings, sauces, marinades, sticks, nutrition bars, baked goods, bread, caramel, steamed grains, meat products, poultry products, meat, poultry, fish, marine protein sources, beans, pasta , sweets, salty snacks, dairy products, cheeses, yoghurts, butter, margarine, ready-to-eat cereals, condiments and sauces and drinks. In particular, the term "beverage" embraces mixtures and concentrates, including, but not limited to, alcoholic and non-alcoholic ready-to-drink beverages and dry powdered beverages. Non-limiting examples of beverages include carbonated beverages, brewed beverages, dairy products, drinking yogurt, milk, coffee creamers, nutritional beverages. Non-limiting examples of animal foods may include: pet food, more specifically dogs and cats, rodent food, small cattle food, cattle food, horse food, and the like.

A third object of the present invention relates to a process for the preparation of compounds of formula (I) such as those defined above.

This method is advantageous in the sense that it is carried out in one step and allows the use of raw materials available in large quantities. The yield of this method is also preferred because it is very high (almost 80%).

The compounds of the present invention are prepared by a cyclization reaction between a cycloalkanone of formula (II) and a thiolic acid of formula (III) in the presence of an acid:

Where:

R ₁ , R ₂ , R ₃ , R ₄ , R ₆ and R ₇ independently represent a hydrogen atom or a methyl group;

R ₅ represents a hydrogen atom or a saturated linear C ₁ -C ₅ alkyl group;

R ₄ and R ₅ may together form a cyclopentyl group;

the total number of carbon atoms is strictly greater than 9.

In a first embodiment, the thiolic acid is thioglycolic acid.

In a second embodiment, the thiolic acid is thiolactic acid.

Preferably the acid used is p-toluenesulfonic acid. Even more preferably, 1-5% molar p-toluenesulfonic acid is used with respect to the reactants. The reaction is carried out in particular at reflux at a temperature in the region of 70° C. in cyclohexane.

Finally, the invention is directed to the use of at least a compound of formula (I) according to the invention as a stereoisomer or a mixture of stereoisomers or a racemic mixture to impart, modify or enhance the organoleptic properties of a substance, composition or product.

By "organoleptic properties" is meant any property that is capable of changing, improving or enhancing the organoleptic perception of a substance, composition, product by the consumer.

In a first embodiment, at least one compound of formula (I) is used as a flavorant, alone or in combination with at least one other odorant and/or at least one solvent, and/or, according to at least one additive. Additional odorants, solvents and additives are known to the person skilled in the art, who can choose the most appropriate depending on the desired effect.

The term "perfume" is used herein to refer to any organoleptic compound that pleasantly stimulates the sense of smell.

The compounds according to the invention can in particular be used as a masking agent or as an odor neutralizing agent. The term "masking agent" or "odor neutralizing agent" refers to the reduction or elimination of the sensation of an unpleasant odor created by one or more molecules that make up the product.

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

Additional flavoring solvents and additives are known to those skilled in the art, who may well choose the more suitable ones depending on the desired effect. The solvents used not only ensure accurate dosing of the compound of the invention in foods and beverages, but also promote even distribution of the compound of the invention in foods and drinks. Suitable solvents can be hydrophilic solvents such as water, propylene glycol, glycerol, ethanol and triacetin, or hydrophobic solvents such as vegetable oils such as palm oil, soybean oil, rapeseed oil, sunflower oil, peanut oil, medium chain triglycerides ( TSC). Medium chain triglycerides are triglycerides based on aliphatic fatty acids containing from 6 to 12 carbon atoms.

By aromatic is meant any use of the compounds of the invention for the flavoring of any liquid or solid human or animal foodstuff, in particular beverages, dairy products, ice cream, as well as for tobacco flavoring applications.

In particular, the compounds of the invention may be used alone or in combination with taste-modulating compounds, ie which alter taste and sensory perception. In any case, the specificity of such taste-modulating compounds lies in the fact that they have no taste and appreciable aromatic properties (no taste and no aroma). Such aroma-modifying compounds may be of synthetic origin or of natural origin.

The following examples illustrate the specific preparation of the compounds of the invention, as well as the olfactory/aromatic profile of each of the exemplary compounds. These examples are 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-THIASPYRO[4.5]DECANE-2-ONE

3,3-dimethylcyclohexanone (the method of which is disclosed, for example, in international application WO 2010043522) is placed in 1.1 equivalents of thioglycolic acid and 4 volumes of cyclohexane. At ambient temperature, 0.05 equivalents of p-toluenesulfonic acid is added. The reaction medium is refluxed and the water formed is removed by azeotropic distillation. When the reaction is complete, the reaction medium is poured into an aqueous solution saturated with sodium bicarbonate. The organic phase is washed with water until neutral pH. After drying over magnesium sulfate, filtering and concentrating, the raw material is distilled under reduced pressure: its boiling point is 89° C. at 0.26 torr.

Description of smell: effect of fruit, peach, raspberry.

Thus obtained 7,7-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one has the following spectral parameters:

¹ H-NMR (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-NMR (75 MHz, CDCl ₃ ): δ (ppm) 172.34; 92.16; 51.31; 39.82; 37.74; 32.23; 31.11; 28.37; 19.90.

MS [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 (clean, cm ^-1 ): 2946m, 1765s, 1455w, 1215m, 1144m, 1060m, 1025m, 993m, 954m, 914w, 811w, 797w, 607w.

EXAMPLE 2: PREPARATION OF 8-ETHYL-1-OXA-4-THIASPYRO[4.5]DECANE-2-ONE

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 raw material, obtained in the form of two diastereoisomers in a ratio of 54:46, is distilled under reduced pressure: its boiling point is 98° C. at 0.18 Torr.

Smell description: exotic fruits, mango, guava, papaya.

8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one thus obtained has the following spectral parameters:

Main isomer (54%):

¹ H-NMR (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-NMR (75 MHz, CDCl ₃ ): δ (ppm) 172.24; 94.34; 38.70; 37.43; 31.69; 39.34; 11.57.

MS [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-NMR (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-NMR (75 MHz, CDCl ₃ ): δ (ppm) 172.26; 91.48; 39.49; 37.17; 32.25; 29.12; 28.69; 11.47.

MS [e/m (%)]: 200(M+, 10), 129(10), 127(100), 109(35), 67(33), 55(42), 46(12), 43(14 ), 41(23).

IR (clean, cm ^-1 ): 2926m, 1767s, 1442w, 1197m, 1139m, 1041m, 966m, 915w, 892w, 854w, 796w.

EXAMPLE 3: PREPARATION OF 8-ETHYL-3-METHYL-1-OXA-4-THIASPYRO[4.5]DECANE-2-ONE

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 equivalent) instead of thioglycolic acid and toluene instead of cyclohexane. The feed, obtained as two diastereoisomers in a ratio of 42:58, is distilled under reduced pressure: its boiling point is 88° C. at 0.4 mbar.

Smell description: peach, herbs, tomato leaf.

Thus obtained 8-ethyl-3-methyl-1-oxa-4-thiaspiro[4.5]decan-2-one has the following spectral parameters:

Main isomer (58%):

¹ H-NMR (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-NMR (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.

MS [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).

Minor isomer (42%):

¹ H-NMR (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-NMR (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.

MS [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-THIASPYRO[4.5]DECANE-2-ONE

8,8-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one is obtained according to the protocol described in example 1, using 4,4-dimethylcyclohexanone instead of 3,3-dimethylcyclohexanone. The raw material is distilled under reduced pressure: it the boiling point is 92°C at 0.39 torr.

Description of smell: fruity, greenery, exotic fruits.

Thus obtained 8,8-dimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one has the following spectral parameters:

¹ H-NMR (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-NMR (75 MHz, CDCl ₃ ): δ (ppm) 172.35; 93.19; 36.05; 35.74; 31.95; 29.11.

MS [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 (clean, cm ^-1 ): 2950m, 1767s, 1444w, 1232m, 1215m, 1156m, 1045s, 1001m, 972m, 877m, 791w, 585w.

EXAMPLE 5: PREPARATION OF 8-PROPYL-1-OXA-4-TIASPIRO[4.5]DECANE-2-ONE

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 raw material obtained in the form of two diastereoisomers in a ratio of 46:54 is distilled under reduced pressure: its boiling point is 106-110°C at 0.2 Torr.

Description of smell: peach, apricot, juicy, pulpy.

Thus obtained 8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one has the following spectral parameters:

Main isomer (54%):

¹ H-NMR (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-NMR (75 MHz, CDCl ₃ ): δ (ppm) 172.38; 94.50; 38.79; 38.27; 31.78; 29.73; 20.12; 14.27.

MS [EI+] (m/z) (%): 214 (M+, 7), 142(10), 141(100), 81(43), 67(20), 55(28), 46(10) , 43(10), 41(18).

Minor isomer (46%):

¹ H-NMR (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-NMR (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 (clean, 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-THIASPYRO[4.5]DECANE-2-ONE

3-methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one is obtained according to the protocol described in example 1, using 4-propylcyclohexanone instead of 3,3-dimethylcyclohexanone, thiolactic acid (1.3 equivalent) instead of thioglycolic acid and toluene instead of cyclohexane. The feed, obtained as two diastereoisomers in a ratio of 44:56, is distilled under reduced pressure: its boiling point is 95° C. at 0.4 mbar.

Description of smell: peach, fruity, green.

Thus obtained 3-methyl-8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one has the following spectral parameters:

Main isomer (56%):

¹ H-NMR (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-NMR (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.

MS [EI+] (m/z) (%): 228 [M+] (3), 142(10), 141(100), 81(20), 67(10).

Minor isomer (44%):

¹ H-NMR (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-NMR (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.

MS [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. OBTAINING OXATHIOLANONE SPIRO[4.5]DECANE-8-ONE

Spiro[4.5]decan-8-one oxathiolanone is prepared according to the protocol described in Example 1, using spiro[4.5]decan-8-one instead of 3,3-dimethylcyclohexanone. The raw material is recrystallized in cyclohexane.

Description of smell: effect of peach, velvety, greenery, vanilla.

The thus obtained spiro[4.5]decan-8-one oxathiolanone has the following spectral parameters:

¹ H-NMR (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-NMR (75 MHz, CDCl ₃ ): δ (ppm) 172.42; 93.38; 41.20; 37.02; 34.68; 32.00; 24.45; 24.39.

MS [EI+] (m/z) (%): 226 (M+, 6), 154(11), 153(100), 135(10), 67(14), 55(15).

IR (clean, 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-THIASPYRO[4.5]DECANE-2-ONE.

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 feed, obtained as two diastereoisomers in a ratio of 74:26, is distilled under reduced pressure: its boiling point is 87° C. at 0.04 torr.

Description of smell: peach, woody, camphor, greenery.

Thus obtained 7,7,9-trimethyl-1-oxa-4-thiaspiro[4.5]decan-2-one has the following spectral parameters:

Main isomer (74%):

¹ H-NMR (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-NMR (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.

MS [EI+] (m/z) (%): 214 (M+, 7), 142(10), 141(100), 123(14), 83(85), 69(15), 55(25) , 46(10), 43(11), 41(22).

Minor isomer (26%):

¹ H-NMR (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-NMR (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.

MS [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 (clean, cm ^-1 ): 2951m, 1766s, 1456w, 1210m, 1167m, 1139w, 1022m, 1005m, 958m, 896w, 859w, 798w, 612w.

EXAMPLE 9 PREPARATION OF 8-PENTYL-1-OXA-4-THIASPYRO[4.5]DECANE-2-ONE

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 feed, obtained as two diastereoisomers in a ratio of 45:55, is distilled under reduced pressure: its boiling point is 135° C. at 0.2 Torr.

Odor Description: Peach, fruity, herbaceous.

Thus obtained 8-pentyl-1-oxa-4-thiaspiro[4.5]decan-2-one has the following spectral parameters:

Main isomer (55%):

¹ H-NMR (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-NMR (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.

MS [EI+] (m/z) (%): 242 (M+, 4), 170(12), 169(100), 95(24), 81(24), 67(12), 55(24) , 43(12), 41(23).

Minor isomer (45%):

¹ H-NMR (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-NMR (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.

MS [e/m (%)]: 242 (M+, 4), 170(12), 169(100), 95(21), 81(21), 67(12), 55(25), 43( 13), 41(23).

IR (clean, cm ^-1 ): 2922m, 2853m, 1769s, 1443w, 1209m, 1184m, 1133w, 1041m, 982m, 901w, 796w.

EXAMPLE 10. PERFUME COMPOSITION CONTAINING THE DERIVATIVES PRODUCED IN EXAMPLES 2, 5 OR 7, INCLUDED IN THE SHAMPOO BASE (IN THE QUANTITY OF 0.6%)

To the rose note batch obtained from the following table (batch A), add:

8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one (compound 16025-37, example 5, lot B)

8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one (compound 16025-43, example 2, lot C)

oxathiolanone spiro[4.5]decan-8-one (compound 16025-56, example 7, lot D)

Components 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 ^ТМ 7 7 7 7 Damascenone 10% DPG 7 7 7 7 Fructone ^ТМ 5 5 5 5 Raspberry Ketone 5 5 5 5 Methyl Phenethyl Ether 10% DPG 5 5 5 5 OKSAN 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

The addition of 5 parts of Compound 16025-37 to Lot A subtly enhances the fruity-pink effect of the lot, giving a more natural petal effect, while the addition of Compound 16025-43 in the same proportions adds more of a woody and peach effect, showing a richer and more rich note of rose. The addition of compound 16026-56 gives a "stronger" green development. There is less rose in the batch than in the two previous cases, more fruit, grapefruit, and even more intensity than in batch A.

In both cases, the addition of a molecule according to the invention imparts an intensity and a green note that pairs well with the base batch of the perfume composition.

EXAMPLE 11. PERFUMERY COMPOSITION CONTAINING THE DERIVATIVES PRODUCED IN EXAMPLES 2, 5 OR 7, INCLUDED IN THE BASIS OF THE SOFTENER (IN THE QUANTITY OF 1%)

To a batch with an exquisite fruity note, obtained in accordance with the following table (batch A), add:

8-propyl-1-oxa-4-thiaspiro[4.5]decan-2-one (compound 16025-37, example 5, lot B)

8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one (compound 16025-43, example 2, lot C)

oxathiolanone spiro[4.5]decan-8-one (compound 16025-56, example 7, lot D)

Components A B C D Hexylcinnamic aldehyde 125 125 125 125 Methyl dihydro jasmonate 80 80 80 80 Ethylvanillin 75 75 75 75 ISO E 45 45 45 45 Hexyl salicylate 45 45 45 45 4-tert-butylcyclohexyl acetate 40 40 40 40 Gabanolide 40 40 40 40 Vanillin 38 38 38 38 Verdyl acetate 35 35 35 35 2-tert-butylcyclohexyl acetate 50% DPG thirty thirty thirty thirty Rosafix 25 25 25 25 Tetrahydrolinalol 25 25 25 25 Anisaldehyde 25 25 25 25 Florol ^ТМ 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 Ethylmethylphenylglycidate 17 17 17 17 Gamma nonalactone 17 17 17 17 Ethyl maltol 14 14 14 14 Silvial ^TM 10% DPG 14 14 14 14 Alpha isomethyl ionone 12 12 12 12 Geranyl acetate 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 frambinon 6 6 6 6 Butyrate DMBC 6 6 6 6 Ethyl cinnamate 6 6 6 6 Maderal ^ТМ 5 5 5 5 Damascenone 10% DPG 5 5 5 5 Liffarome ^TM 10% DPG 5 5 5 5 Ethyl methyl valerate 10% DPG 4 4 4 4 Delta Damascon 4 4 4 4 Heliotropin 4 4 4 4 Cyclogalbanate ^TM 10% DPG 4 4 4 4 Patchouli EM 2 2 2 2 6-[2,4,4-trimethyl-cyclopentylidene]-hexanal 1% DPG 2 2 2 2 Orcanox ^ТМ 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

The addition of 3 parts Compound 16025-37 to the A batch brings a lot of intensity and more of a melding green note, while the addition of Compound 16025-43 rounds the note even more, with a more inherent and intense gourmet vanilla effect.

The addition of compound 16025-56 also rounds out the batch while flattening the fruity notes to this dosage.

EXAMPLE 12 AROMATIC COMPOSITION CONTAINING THE DERIVATIVE OF EXAMPLE 5 INCLUDED IN YOGURT (AT 0.08%, ie 160 PPB)

Components A B Acetylmethylcarbinol 50% PG 2 2 Strawberry furanon 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 CO2 acetic acid 20 20 ethyl acetate 20 20 Linalol 25 25 C05 2-Methylbutyric acid 25 25 Apricot B.P.L. 48.5 48.5 propylene glycol 796 794.5 Compound 16025-37 10% PG - 2 1000 1000

The addition of compound 16025-37 at 160ppb to the yogurt gives the peach flavor a more authentic, rounder peach nectar profile.

EXAMPLE 13 AROMATIC COMPOSITION CONTAINING THE DERIVATIVE OF EXAMPLE 5 INCLUDED IN YOGURT (AT 0.02%, ie 140 PPB)

Components A B Butyric acid 15 15 Gamma decalactone 7 7 CO2 acetic acid 12 12 Linalol 1.5 1.5 C05 2-Methylbutyric acid 6 6 ISOPROPYL METHYLTHIAZOL 1% ALC 1 1 Buchu essential oil diterpene 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 cis-3-hexenol 4.5 4.5 cis-3-hexenyl acetate 9 9 Limonene 9 9 Isoamyl acetate 15 15 CO2 ethyl alcohol 899.1 897.1 Compound 16025-37 10% PG - 7 1000 1000

The addition of compound 16025-37 at 140ppb complicates the profile of the apricot, brings a very natural appearance, apricot pulp, juice, very good taste. This apricot flavor profile is very specific and cannot be reproduced using other prior art compounds.

EXAMPLE 14: OLFATOMETRIC TESTS

It is generally accepted that the ratio of volatility to odor detection threshold provides a "smell number" without a unit of measure, taking into account the olfactory intensity of the molecule. The larger this numerical value, the more intense is the molecule in question. To calculate this odor number, the volatility must be determined as well as the threshold of detection.

In the present study, two molecules of the invention are tested to determine their intensity (via their odor number) relative to a prior art control molecule, gamma-undecalactone. The two test molecules of the invention are those from Example 2 (8-ethyl-1-oxa-4-thiaspiro[4.5]decan-2-one) and Example 5 (8-propyl-1-oxa-4-thiaspiro[4.5]decane -2-on).

Initially determine the value of volatility at 20°C of the molecules from example 2 and example 5 by ebulliometry. These values are respectively 19.8 μg.l ^-1 and 7.8 μg.l ^-1 .

Secondly, psychosensory studies were carried out to determine the detection threshold of the two molecules of the present invention, as well as gamma-undecalactone.

The detection threshold numerical value is obtained using a dynamic olfactometer constructed according to the guidelines of ISO 13725 and ISO 13301. It corresponds to the critical statistical concentration of a gaseous substance to elicit a positive response from a panel of at least eighteen experts ranging in age from 22 to 57 years according to the forced-choice-of-two model. One of these options is a controlled dilution of the raw material-laden airflow, and the other choice is a neutral airflow. Randomly repeating these choices for a set of five to eight gaseous concentrations, respectively, makes it possible to determine the threshold of detection after statistical processing of the obtained data. Thus, the detection threshold for the molecules from Example 2 and Example 5 was determined to be 0.016 ng.l ^-1 and 0.075 ng.l ^-1 respectively.

Therefore, after these measurements, it is possible to calculate the numerical value of the odor of the molecules according to the invention compared to gamma-undecalactone.

Odor value=Volatility value/detection threshold

The odor number is 1222223 for the molecule of Example 2 and 104133 for the molecule of Example 5. However, for gamma-undecalactone, the odor number, determined under identical experimental conditions, is 5473.

In conclusion, the numerical value of the odor of the molecules of the invention (Examples 2 and 5) is quite clearly greater than that of gamma-undecalactone, indicating that said molecules of the invention are quite clearly more intense than gamma-undecalactone.

In addition, the substantivity, assessed by the experts, is 2.59 for the molecule of example 2 and 2.62 for the molecule of example 5.

Claims (32)

1. Compound of the following general formula (I)

(I) where R ₁ , R ₂ , R ₃ , R ₄ , R ₆ and R ₇ independently represent a hydrogen atom or a methyl group; R ₅ represents a hydrogen atom or a saturated linear C ₁ -C ₅ alkyl group; R ₄ and R ₅ may together form a cyclopentyl group; the total number of carbon atoms is strictly greater than 9. 2. The compound according to claim 1, characterized in that R ₅ is a saturated linear C ₁ -C ₅ alkyl group. 3. The compound according to claim 1 or 2, characterized in that R ₁ , R ₂ , R ₃ , R ₄ , R ₆ and R ₇ represent a hydrogen atom. 4. The connection according to one of paragraphs. 1-3, characterized in that the total number of carbon atoms is 10 or 11. 5. A compound according to one of the preceding claims, characterized in that it 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, oxathiolanone 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 -she. 6. Composition for imparting, changing or enhancing the organoleptic properties of a substance, composition or product, containing an effective amount of at least one compound of the following general formula (I):

, where R ₁ , R ₂ , R ₃ , R ₄ , R ₆ and R ₇ independently represent a hydrogen atom or a methyl group; R ₅ represents a hydrogen atom or a saturated linear C ₁ -C ₅ alkyl group; R ₄ and R ₅ may together form a cyclopentyl group; the total number of carbon atoms is strictly greater than 9, and an inert support material. 7. Composition according to claim 6, said composition contains 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, oxathiolanone 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] dean-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 from 0.000001 to 50 wt.% in relation to the total weight of the composition, more specifically from 0.000005 to 20 wt. %. 9. Composition according to one of paragraphs. 6-8, characterized in that it is a perfume composition containing at least one compound of formula (I) and at least one other flavoring substance. 10. The composition according to one of paragraphs. 6-8, characterized in that it is a composition for aromatization containing at least one compound of formula (I) and at least one other substance for aromatization. 11. The method of obtaining compounds of formula (I), such as described in paragraphs. 1-5 by a cyclization reaction between a cycloalkanone of formula (II) and a thiolic acid of formula (III) in the presence of an acid

where R ₁ , R ₂ , R ₃ , R ₄ , R ₆ and R ₇ independently represent a hydrogen atom or a methyl group; R ₅ represents a hydrogen atom or a saturated linear C ₁ -C ₅ alkyl group; R ₄ and R ₅ may together form a cyclopentyl group; the total number of carbon atoms is strictly greater than 9. 12. The method of claim 11 wherein the thiolic acid is thioglycolic acid. 13. The method according to p. 11, characterized in that the thiolic acid is thiolactic acid. 14. The method according to one of paragraphs. 11-13, characterized in that p-toluenesulfonic acid is used as the acid. 15. The use of at least one compound of General formula (I), such as defined in paragraphs. 1-5 as a stereoisomer, or a mixture of stereoisomers, or a racemic mixture to impart, modify or enhance the organoleptic properties of a substance, composition or product. 16. The use according to claim 15 of at least one compound of formula (I) as a fragrance, alone or in combination with at least one other odorant and/or at least one solvent, and/ or at least one additive. 17. Use according to claim 15 of at least one compound of general formula (I) as a flavoring compound, alone or in combination with at least one other flavoring agent and/or at least one solvent, and/or at least one additive.