WO2025224221A1 - Drimane compound and its use as an aroma chemical - Google Patents

Abstract

The present invention relates to the compound 2,6,6-trimethyl-12-methylene-10- thiatricyclo[7.2.1.0^2,7]dodecane and to the compound 2,6,6-trimethyl-12-methylene-10λ⁶- thiatricyclo[7.2.1.0^2,7]dodecane-10,10-dioxide, which is suitable as intermediate for the preparation of 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0^2,7]dodecane. The invention further relates to a process for the preparation of 2,6,6-trimethyl-12-methylene- 10-thiatricyclo[7.2.1.0^2,7]dodecane. In addition, the invention relates to the use of 2,6,6- trimethyl-12-methylene-10-thiatricyclo[7.2.1.0^2,7]dodecane as an aroma chemical and to a composition comprising 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0^2,7]dodecane and a further aroma chemical and/or a carrier. The invention further relates to the use of 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0^2,7]dodecane to impart an aroma note to a composition.

Description

Drimane compound and its use as an aroma chemical

Description

The present invention relates to the compound 2,6,6-trimethyl-12-methylene-10- thiatricyclo[7.2.1.0²'⁷]dodecane and to the compound 2,6,6-trimethyl-12-methylene-10A⁶- thiatricyclo[7.2.1.0²'⁷]dodecane-10,10-dioxide, which is suitable as intermediate for the preparation of 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane. The invention further relates to a process for the preparation of 2,6,6-trimethyl-12-methylene- 10-thiatricyclo[7.2.1.0²'⁷]dodecane. In addition, the invention relates to the use of 2,6,6- trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane as an aroma chemical and to a composition comprising 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane and a further aroma chemical and/or a carrier. The invention further relates to the use of 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane to impart an aroma note to a composition.

BACKGROUND OF THE INVENTION

Aroma chemicals, especially fragrances, are of great interest in the field of cosmetics and cleaning and laundry compositions. Fragrances of natural origin are mostly expensive, often limited in their availability and, on account of fluctuations in environmental conditions, are also subject to variations in their content, purity etc. To circumvent these undesirable factors, it is therefore of great interest to create synthetic substances which have sensory properties that resemble more expensive natural fragrances, or which have novel and interesting sensory profiles.

US 2012/0183490 discloses 6-methyl-2-butyl-l,3-oxathiane compounds for enhancing the flavor of a fragrance composition.

WO 2022/073845 discloses l-(3-isobutylphenyl)ethanone, l-(3-isobutylphenyl)ethanol and derivatives thereof for imparting an aroma impression to a composition.

WO 2022/129167 discloses certain bicyclic compounds, such as 3,3,8,8-tetramethyl-

4.5.6.7-tetrahydro-2H-napthalene-l-one, 4,4,8,8-tetramethyl-9-methylene-bicyclo[3.3.1] nonan-2-one, 3,3,7,7-tetramethyl-2,4,5,6-tetrahydroinden-l-one, 3,3,8,8-tetramethyl-

1.2.4.5.6.7-hexahydronapthalene-l-ol, 4,4,8,8-tetramethyl-9-methylene-bicyclo[3.3.1] nonan-2-ol, 3,3,7,7-tetramethyl-2,4,5,6-tetrahydro-lH-inden-l-ol, and mixtures thereof for imparting an aroma impression to a composition.

Despite a large number of already existing aroma chemicals, there is a constant need for new components in order to be able to satisfy the multitude of properties desired for extremely diverse areas of application. These include, firstly, the sensory properties, i.e. the compounds should have advantageous odiferous (olfactory) or gustatory properties. Furthermore, aroma chemicals should also have additional positive secondary properties, such as e.g. an efficient preparation method, the possibility of providing better sensory profiles as a result of synergistic effects with other aroma chemicals, a higher stability in a wide range of compositions as well as under certain application conditions, a higher extendibility and/or a better staying power.

There is an increased need for aroma chemicals which can impart an aroma impression, especially a fruity and/or a woody and/or a citrus and/or a fresh odiferous impression to a composition. Such properties are of special interest for compositions such as for example body care compositions, hygiene articles, cleaning compositions, textile detergent compositions and compositions for scent dispensers. Of special interest are aroma chemicals, which can impart one or more distinct aroma impressions to a composition, thereby contributing to a rich and interesting sensory profile, especially an olfactory profile of the composition. In addition, especially regarding aroma chemicals which can impart an aroma impression, the substantivity as well as the tenacity are of special interest in order to obtain a long-lasting odiferous impression in the composition as well as to the surface with which the composition is treated.

It is an object of the present invention to provide an aroma chemical, which can impart an aroma impression, especially a fruity note and/or a woody note and/or a citrus note and/or a fresh note and/or an animalic note.

It is further an object of the present invention to provide an aroma chemical, which can impart a long-lasting aroma impression, especially a fruity note and/or a woody note and/or a citrus note and/or a fresh note and/or an animalic note to compositions as well as to surfaces, such as for example of the skin or of textiles, treated with such compositions, and which is stable in a wide variety of compositions.

SUMMARY OF THE INVENTION

It was surprisingly found that the above objectives are achieved with the drimane compound 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane, as it is able to impart an aroma impression, especially a citrus note, a woody note, a fruity note, a fresh note, an animalic note or a combination thereof.

The present invention therefore relates to the compound 2,6,6-trimethyl-12-methylene- 10-thiatricyclo[7.2.1.0²'⁷]dodecane, i.e. the compound of the following formula: The compound 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane is hereinafter also referred to as compound I.

The present invention further relates to the compound 2,6,6-trimethyl-12-methylene- 10A⁶-thiatricyclo[7.2.1.0²'⁷]dodecane-10,10-dioxide, which is suitable as an intermediate for preparing 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane. The compound 2,6,6-trimethyl-12-methylene-10A⁶-thiatricyclo[7.2.1.0²'⁷]dodecane-10,10- dioxide is hereinafter also referred to as compound II.

The invention also relates to a process for the preparation of compound I which comprises reacting compound II with a reducing agent.

The invention also relates the use of compound I as an aroma chemical and to a composition comprising compound I and a further aroma chemical and/or a carrier.

The present invention in addition relates to the use of compound I to impart an aroma note to a composition.

The invention is associated with several benefits. 2,6,6-Trimethyl-12-methylene-10-thiatri- cyclo[7.2.1.0²'⁷]dodecane, i.e. compound I, is a stable, readily accessible compound which can beneficially be used as an aroma chemical, as it is able to impart one or more distinct aroma impressions to a composition as well as to surfaces treated with such a composition, such as for example skin and textiles.

Compound I is in particular able to impart a long-lasting aroma impression, especially an aroma impression having a fruity note and/or a woody note and/or a citrus note and/or a fresh note and/or an animalic note. These specific aroma impressions are highly sought after and consequently there is a high demand for aroma chemicals, such as compound I, that are able to impart these impressions.

DETAILED DESCRIPTION OF THE INVENTION

The compound 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane, i.e. compound I, has four stereocenters, which are the bridgeheads of its molecule, i.e. the carbon atoms in the positions 1, 2, 7 and 9, which independently of one another can be R- or S-configurated.

Therefore, compound I may exist in the form of one of its 16 stereoisomers or in the form of any mixture of these stereoisomers. For steric reasons, the CH₂-S moiety is preferably s -connected to positions 1 and 9 of the tricyclus. Consequently, compound I may preferably exist in the form of 8 stereoisomers or mixtures thereof. The compound I may therefore theoretically exist as 8 pairs of enantiomers, in particular as less strained 4 pairs of enantiomers. The compound I may also exist as racemic mixtures of one or more particular pairs of said 8 pairs of enantiomers or as non-racemic mixtures of such particular pairs. The present invention thus relates to any one of the pure pairs of enantiomers, to particular enantiomers of the compound I as well as to any mixture of these stereoisomers.

The four most preferred stereoisomers of the compounds of the formula (I) are the compounds (la) to (Id) are depicted in scheme 1 below.

Scheme 1

(lS,2R,7R,9R)-2,6,6-Trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²-⁷]dodecane

Compound la

(lR,2S,7S,9S)-2,6,6-Trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²-⁷]dodecane

Compound lb

(lS,2S,7R,9R)-2,6,6-Trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane

Compound Ic

(lR,2R,7S,9S)-2,6,6-Trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane

Compound Id Preferred stereoisomers of compound I in the sense of this invention have syn- configuration of the tetrahydrothiophene ring and the angular methyl group at position 2, similar to many natural products (Y Huang, Vialante V, ChemBioChem 2022, 23, e202200173), e.g., compounds la and lb. The preferred compounds may be present as a pure enantiomer, or a mixture of enantiomers, or as a racemate two of two of said stereoisomers. For example, the compounds la and lb may be present as the pure enantiomer la or lb or be present as a non-racemic mixture of the compounds la and lb or as a racemic mixture of the compounds la and lb.

More preferred stereoisomers of compound I in the sense of this invention have anti- configuration of the tetrahydrothiophene ring and the angular methyl group at position 2 , e.g., compound Ic and Id. The more preferred compounds may be present as a pure enantiomer, or a mixture of enantiomers, or as a racemate two of two of said stereoisomers. For example, the compounds la and lb may be present as the pure enantiomer Ic or Id or be present as a non-racemic mixture of the compounds Ic and Id or as a racemic mixture of the compounds Ic and Id.

Here and in the following, the synl anti notation refers to the IUPAC nomenclature - see https://goldbook.iupac.org/terms/view/E02094

Likewise, the four bridgehead carbon atoms of the compound 2,6,6-trimethyl-12- methylene-10A⁶-thiatricyclo[7.2.1.0²'⁷]dodecane-10,10-dioxide, i.e. compound II, represent its four stereocenters, which independently of one another can be R- or S- configurated.

Compound II therefore may exist in the form of one of its 16 stereoisomers, in particular in the form of one of its sterically less strained 8 stereoisomers, or in the form of any mixture of these stereoisomers. Consequently, compound II may exist as a racemic mixture or as a non-racemic mixture of one of its 8 pairs, in particular its 4 pairs of enantiomers or as any combination of these mixtures. The compound II may also exist as a racemic mixtures of one or more particular pairs of said 8 pairs of enantiomers or as non-racemic mixtures of such particular pairs.. The present invention thus relates to any one of the pure pairs of enantiomers, to particular enantiomers of the compound II as well as to any mixture of these stereoisomers.

Preferred stereoisomers of the compound of the formula (II) are those, which have syn- configuration of the tetrahydrothiophenedioxide ring and the angular methyl group at position 2, in particular the stereoisomers Ila and lib which have the same configuration at Cl, C2 and C2 as the compounds la and lb depicted in scheme 1 above.

Also preferred stereoisomers of the compound of the formula (II) are those, which have ^/-configuration of the tetrahydrothiophenedioxide ring and the angular methyl group at position 2, in particular the stereoisomers lie and lid which have the same configuration at Cl, C2 and C2 as the compounds Ic and Id depicted in scheme 1 above.

In the context of the present invention, the term "aroma" refers to a sensory property and comprises an odor and/or a flavor.

The term “aroma chemical” denotes a substance which is used to obtain a sensory or organoleptic (used interchangeably herein) impression and comprises its use to obtain an olfactory and/or a flavor impression. The term "olfactory impression" denotes an odor impression without any positive or negative judgement, while the term "scent impression" or "fragrance impression" (used interchangeably herein) as used herein is connected to an odor impression which is generally felt as pleasant. Thus a "fragrance" or "scent" denotes an aroma chemical, which predominately induces a pleasant odor impression. A flavor induces a taste impression.

The term "aroma composition", as used herein, refers to a composition which induces an aroma. The term aroma composition comprises "odor composition" and/or "flavor composition". An odor composition is a composition which predominately induces an odor impression, and a flavor composition is a composition which predominantly induces a taste impression.

The term odor composition comprises "fragrance composition" or "scent composition" (used interchangeably herein), which predominately induce an odor impression which is generally felt as pleasant.

General expressions such as "advantageous sensory properties" or "advantageous organoleptic properties" describe the niceness and conciseness of an organoleptic impression conveyed by an aroma chemical. "Niceness" and "conciseness" are terms which are familiar to the person skilled in the art, such as a perfumer. Niceness generally refers to a spontaneously brought about, positively perceived, pleasant sensory impression. However, "nice" does not have to be synonymous with "sweet". "Nice" can also be the odor of musk or sandalwood. "Conciseness" generally refers to a spontaneously brought about sensory impression which - for the same test panel - brings about a reproducibly identical reminder of something specific. For example, a substance can have an odor which is spontaneously reminiscent of that of an "apple": the odor would then be concisely of "apples". If this apple odor were very pleasant because the odor is reminiscent, for example, of a sweet, fully ripe apple, the odor would be termed "nice". However, the odor of a typically tart apple can also be concise. If both reactions arise upon smelling the substance, in the example thus a nice and concise apple odor, then this substance has particularly advantageous sensory properties. The term "tenacity" describes the evaporation behavior over time of an aroma chemical. The tenacity can for example be determined by applying the aroma chemical to a test strip, and by subsequent olfactory evaluation of the odor impression of the test strip. For aroma chemicals with high tenacity the time span after which the panel can still identify an aroma impression is long.

The term "substantivity" describes the interaction of an aroma chemical with a surface, such as for example the skin or a textile, especially after subsequent treatment of the surface, such as for example washing. The substantivity can for example be determined by washing a textile with a textile detergent composition comprising the aroma chemical and subsequent olfactory evaluation of the textile directly after washing (wet textile) as well as evaluation of the dry textile after prolonged storage.

The term "stability" describes the behavior of an aroma chemical upon contact with oxygen, light and/or other substances. An aroma chemical with high stability maintains its aroma profile over a long period in time, preferably in a large variety of compositions and under various storage conditions.

The remarks made below concerning preferred embodiments concerning the process for preparing the compound I, the uses of the compound I and the aroma compositions comprising the compound I are valid on their own as well as preferably in combination with each other.

The process of the present invention for preparing the compound 2,6,6-trimethyl-12- methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane, i.e. compound I, comprises the step of reacting of 2,6,6-trimethyl-12-methylene-10A⁶-thiatricyclo[7.2.1.0²'⁷]dodecane-10,10- dioxide, i.e. compound II, with a reducing agent (reductant). In this step, hereinafter also referred to as step A, the compound II is converted into the desired compound I by reduction of its sulfonyl group (-SO₂-) to the sulfanyl group (-S-), as shown in scheme 2 below.

Compound II is used as starting material in step A of the process of the invention in the form of one of its pure diastereomers or in the form of a mixture of 2 to 16 diastereomers, and preferably is used as a mixture of 2 to 5, especially 2 to 4, of its diastereomers. Preferred reducing agents for the transformation in step A are samarium(II) iodide and complex hydrides which are preferably selected from the group consisting of aluminum hydrides, such as diisobutylaluminum hydride ((ABu₂AIH)₂), lithium aluminum hydride (LiAIH₄) or sodium aluminum hydride (NaAIH₄), and borohydrides, such as lithium borohydride (LiBH₄) and sodium borohydride (NaBH₄). Preference is given to the use of an aluminum hydrides as reducing agent, such as in particular lithium aluminium hydride. In case, samarium(II) iodide is used as reductant in step A, the reaction is preferably carried out using hexamethylphosphoramide (HMPT) as solvent.

In the reaction of step A the reducing agent, is typically used in at least equimolar amounts or preferably in excess with respect to the stoichiometry of the reaction. In case of complex hydrides, such as for instance LiAIH₄, the reducing agent is preferably used in an amount of at least 1 mol, in particular at least 3 mol, more preferably at least 5 mol or at least 8 mol, e. g. in amounts in the range of 1 to 25 mol, more preferably of 3 to 21 mol, even more preferably of 5 to 19 mol and especially of 8 to 18 mol, based in each case on 1 mol of the compound II and calculated with respect to the metal atom in the complex hydride.

Typically, the reduction in step A is carried out in the presence of an organic solvent. Depending on the type of reducing agent used in step A, the solvent may be selected from protic solvents, aprotic organic solvents and mixtures of these solvents with one another. Suitable protic solvents in this context are preferably selected from the group consisting of water, Ci-Ce-alkanols, such as methanol, ethanol, isopropanol or n-butanol, ethylene glycol, propylene glycol, glycerol and mixtures thereof. Suitable aprotic organic solvents here are preferably selected from the group consisting of ethers, such as aliphatic C₂-Cio-ethers, for example diethyl ether, dipropyl ether, methyl isobutyl ether, tert-butyl methyl ether, di-n-butyl ether or tert-butyl ethyl ether, alicyclic C₄-C₆-ethers, such as tetra hydrofuran (THF), tetra hydropyran, 2-methyltetrahydrofuran, 3- methyltetrahydrofuran or 1,4-dioxane, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) and hexamethylphosphoramide (HMPT).

In another embodiment of the invention the reduction in step A is conducted in the absence of a solvent.

In particular preferred embodiment of the invention the reduction in step A is carried out in an aprotic organic solvent or solvent mixture. The aprotic organic solvent preferably comprise at least one organic solvent of the group of ethers, in particular aliphatic C₂-Cio- ethers, such as diethyl ether, di-n-propyl ether, diisopropyl ether, methyl isobutyl ether, tert-butyl methyl ether or di-n-butyl ether, and alicyclic C₄-C₆-ethers, such as tetrahydrofurane (THF) or 1,4-dioxane, and mixtures thereof. The reductive conversion of compound II into compound I in step A of the process according to the invention is carried out by bringing compound II into contact with a reductant. In a preferred embodiment it has been found to be beneficial to initially charge the reaction vessel with the reducing agent in dispersed form or in dissolved form, and then to add compound II, which is employed as such or preferably in dissolved form.

The reaction of step A is typically effected in a reaction vessel with stirring apparatus. The reaction temperature of reaction in step A depends on different factors, in particular on the reactivity of the reductant used, and can be determined by the person skilled in the art in the individual case, for example by simple preliminary tests. In general, the conversion is performed at a temperature in the range from -10 to 100°C, preferably in the range from -10 to 80°C, more preferably in the range from -5 to 70°C and specifically in the range from 0 to 50°C.

According to a preferred embodiment of the invention the reaction in step A is initiated at a lower temperature, for instance -10°C, preferably -5°C, more preferably 0°C and especially 3°C, and after the complete addition of the compound II the temperature is increased to a temperature of for instance 100°C, preferably 80°C, more preferably 70°C and especially 50°C.

Upon completion or near completion of the reductive conversion in step A the reaction mixture is typically subjected to work-up measures well established in the art. Generally, the excess of the reducing agent still present is deactivated in an initial step. If a complex hydride is used as the reducing agent, this can be done by adding an salt containing crystal water, such as e.g. the decahydrate of sodium sulfate (Na₂SO₄ x 10 H₂O), after cooling the reaction mixture, e. g. to a temperature of about -10 to 15°C. The mixture is allowed to react until the hydrogen formation ceases. The reaction mixture may then be subjected to a separation of the deactivated reductant from the compound (I), e. g. by filtration and separating of the solvent. The crude compound (I) thus obtained may then be subjected to further purification steps, such as in particular preparative reversed phase HPLC using a C-18-modified stationary phase. This way the compound I can be obtained in at least sufficient purity in the form of a single one of its diastereomers or in the form of a mixture of 2, 3 or 4 of its diastereomers.

The process of the present invention for preparing the compound 2,6,6-trimethyl-12- methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane, i.e. compound I, may additionally comprise the provision of the compound II, i.e. 2,6,6-trimethyl-12-methylene-10A⁶-thiatricyclo- [7.2.1.0²'⁷]dodecane-10,10-dioxide. Surprisingly, the compound (II) can be prepared by treating 2-[3,7-dimethylocta-2,6-dienyl]-3-methyl-2,5-dihydrothiophene-l,l-dioxide with an acid. In this step, hereinafter also referred to as step B, the compound 2-[3,7- dimethylocta-2,6-dienyl]-3-methyl-2,5-dihydrothiophene-l,l-dioxide, hereinafter also referred to as compound III, is cyclized to compound II. Without being bound by theory, it is believed that this cyclization reaction proceeds via the intermediate III', as shown in scheme 3 below.

Scheme 3 intermediate III

Compound III contains a stereocenter in position 2 of its heterocycle, which may be R- or S-configured. Compound III thus comprises 2 stereoisomers which all can be cyclized to the desired compound II.

For reasons discussed herein below, the starting material used in the cyclization step B may or may not contain, in addition to compound III, larger amounts of 3-[4,8- dimethylnona-3,7-dienyl]-2,5-dihydrothiophene-l,l-dioxide, hereinafter also named compound IV. However, this compound does not cyclize under the reaction conditions of step B and can be separated off from the desired cyclization product, i.e. compound II, following the cyclization reaction. Alternatively, compound IV can be removed from said mixture of compounds III and IV prior to the cyclization step B using suitable purification measures to obtain a pure or almost pure compound III.

Compound III may be used in the form of one of its pure stereoisomers or in the form of a mixture of its 2 stereoisomers as starting material in step B of the process of the invention. Preferably, compound III is used as starting material in step B in the form of a mixtures of its 4 stereoisomers.

Thus, in one embodiment of the invention the compound III preparation used as starting material in step B of the process of the invention comprises compound III in the form of one of its stereoisomers or in the form of a mixture of 2 to 4 of its stereoisomers and 0 to less than 5% by weight, preferably 0 to 2% by weight and in particular 0 to 1% by weight of compound IV.

In another embodiment of the invention the compound III preparation used as starting material in step B of the process of the invention comprises compound III in the form of one of its stereoisomers or in the form of a mixture of 2 of its stereoisomers and 5 to 70% by weight, preferably 10 to 50% by weight and in particular 20 to 40% by weight of compound IV. The acid used for the transformation in step B is generally a Broensted acid, a Lewis acid or a mixture of both.

In a particular embodiment of the invention the acid used in the transformation of step B is a Broensted acid. Suitable Broensted acids include for example, mineral acids, such as sulfuric acid, nitric acid, phosphoric acid, phosphorous acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and hydrofluoric acid, silicic acid, boric acid or perchloric acid, organic sulfonic acids, e. g. aliphatic sulfonic acids, such as methanesulfonic acid and trifluoromethanesulfonic acid, and aromatic sulfonic acids, such as p-toluenesulfonic acid and benzenesulfonic acid, carboxylic acids, such as trifluoroacetic acid, and heterogenic acids, such as acidic cationic exchange resins, acidic montmorillonites or acidic bentonites, and mixtures of these acids with one another. Particularly preferred Broensted acids here are sulfuric acid, hydrochloric acid, p- toluenesulfonic acid, methansulfonic acid and trifluoromethanesulfonic acid and acidic cation exchange resins.

In another particularly preferred embodiment of the invention the acid used in step B is a Lewis acid which is preferably selected from boron trifluoride and boron trifluoride complexes, such as boron trifluoride etherates or boron trifluoride-methanol complex, aluminum trichloride, titanium tetrachloride, tris(pentafluorophenyl)borane, tin tetrachloride and mixtures of these acids with one another. Particularly preferred Lewis acids here are boron trifluoride and boron trifluoride etherates. Boron trifluoride etherates are complexes of boron trifluoride with an ether, e. g. an aliphatic ether such as diethylrether or and alicyclic ether, such as THF.

In another particular embodiment of the invention the acid used in step B is a mixture comprising at least one Broensted acid and at least one Lewis acid, where the Bronsted and Lewis acids are preferably selected from those listed above.

Particular preference is given to using as the acid in the conversion of step B a Lewis acid, which is especially boron trifluoride or a boron trifluoride complex, such as in particular boron trifluoride etherate.

In the reaction of step B the acid, such as for instance boron trifluoride etherate, is preferably used in an amount of 0.01 to 8 mol, more preferably of 0.1 to 5 mol, even more preferably of 0.5 to 4 mol, in particular of 1 to 3 mol and especially of 1.5 to 2.5 mol, based in each case on 1 mol of the compound III.

In one embodiment of the invention the cyclization in step B is conducted in the presence of a solvent which is preferably selected from protic solvents, polar aprotic solvents and mixtures of these solvents with one another. Suitable protic solvents in this context are preferably selected from the group consisting of water, Ci-C₆-alkanols, such as methanol, ethanol, isopropanol or n-butanol, perfluoroalcohols, such as hexafluoroisopropanol or nonafluoro-tert-butanol, ethylene glycol, propylene glycol and mixtures thereof. Suitable polar aprotic solvents here are preferably selected from the group consisting of halogenated Ci-C4-alkanes, such as dichloromethane, chloroform, 1,1-dichloroethane, 1,2- dichloroethane or 1,1,1-trichloroethane, Ci-C4-nitroalkanes, such as nitromethane, nitroethane or 2-nitropropane, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), N- methyl-2-pyrrolidone (NMP) and acetonitrile.

In another embodiment of the invention the cyclization in step B is conducted in the absence of a solvent.

In particular preferred embodiment of the invention the cyclization in step B is conducted in the presence of a polar aprotic organic solvent that is preferably selected from C1-C3- nitroalkanes, such as nitromethane or 2-nitropropane, DMF, acetonitrile and mixtures thereof.

Particular preference is given to using acetonitrile as solvent for the conversion in step B.

The conversion of compound III by cyclization into compound II in step B of the process according to the invention is carried out by bringing compound III into contact with an acid, especially a Lewis acid, such as boron trifluoride etherate. It has been found to be beneficial to initially charge the reaction vessel with the compound III in dispersed form or preferably in dissolved form, and then to add the acid, which may be employed as such or in dissolved form, and is preferably added as such in neat form.

The reaction of step A is typically effected in a closed or preferably in an open reaction vessel with stirring apparatus. The conversion is typically performed with stirring at a temperature in the range from -20 to 100°C, preferably in the range from -10 to 80°C, more preferably in the range from 0 to 50°C and specifically in the range from 10 to 35°C.

Upon completion or near completion of the cyclization in step B the reaction mixture is typically subjected to work-up measures well established in the art. In general, the reaction mixture is initially reduced to dryness by evaporation. The obtained residue may then subjected to a standard aqueous workup procedure and subsequently further purified e.g. by chromatography or distillation. Alternatively, the initially obtained residue can be submitted without prior aqueous workup to chromatographic purification, such as in particular preparative reversed phase HPLC using a C-18-modified stationary phase. The above purification steps by means of chromatography or distillation may be particularly useful to separate the desired compound II from the compound IV if, as previously discussed, this impurity was present to a greater extent in the compound III used as starting material. This way compound II can be obtained in at least sufficient purity in the form of a single one of its stereoisomers or typically in the form of a mixture of at least 2 of its preferred stereoisomers, in particular in the form of mixtures of at least 2 of the compound (Ila) - (lid).

The process of the present invention for preparing the compound 2,6,6-trimethyl-12- methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane, i.e. compound I, additionally comprises the provision of compound III, i.e. 2-[3,7-dimethylocta-2,6-dienyl]-3-methyl-2,5- dihydrothiophene-l,l-dioxide, by a reaction step in which a-farnesene is reacted with sulfur dioxide. In this step, hereinafter also referred to as step C, a-farnesene is converted into the compound III, as shown in scheme 4 below.

Scheme 4 a-Farnesene, i.e. 3,7,ll-trimethyl-l,3,6,10-dodecatetraene can exist as four stereoisomers that differ about the geometry of two double bonds at the positions 3 and 6. The a-farnesene preparation used as starting material in reaction step C of the process according to the invention may therefore contain a-farnesene in the form of a single one of its stereoisomers or preferably in the form of a mixture of 2 to 4 of the stereoisomers. In addition, commonly available grades of a-farnesene frequently are mixtures of a- farnesene with p-farnesene, i.e. 7,ll-dimethyl-3-methylene-l,6,10-dodecatriene. From these mixtures, a-farnesene can be obtained in the desired purity e.g. by distillation or chromatography. Alternatively, these mixtures can also be used directly as starting material for the reaction in step C. In the latter case, p-farnesene reacts with sulfur dioxide in step C of the process according to the invention to give a different dihydrothiophene product than a-farnesene, namely the previously mentioned compound IV, i.e. 3-[4,8-dimethylnona-3,7-dienyl]-2,5-dihydrothiophene-l,l-dioxide. Following the conversion of step C the unwanted compound IV may be separated off the desired compound III by appropriate purification measures, such as particularly distillation or chromatography. Alternatively, the mixture of compounds III and IV may be directly subjected to the cyclization in step B of the process of the invention and the intended tricyclic compound II can then be isolated by removing the unreacted compound IV, as already described above.

Thus, in one embodiment of the invention the a-farnesene preparation used as starting material in step C of the process of the invention comprises a-farnesene in the form of one of its stereoisomers or in the form of a mixture of 2 to 4 of its stereoisomers and 0 to less than 5% by weight, preferably 0 to 2% by weight and in particular 0 to 1% by weight of p-farnesene.

In another embodiment of the invention the a-farnesene preparation used as starting material in step C of the process of the invention comprises a-farnesene in the form of one of its stereoisomers or in the form of a mixture of 2 to 4 of its stereoisomers and 5 to 70% by weight, preferably 15 to 60% by weight and in particular 25 to 50% by weight of p-farnesene.

In the reaction of step C of the process of the invention the reactant sulfur dioxide is preferably used in an amount of 0.5 to 30 mol, more preferably 1 to 20 mol, even more preferably 2 to 17 mol and especially 5 to 15 mol, based in each case on 1 mol of farnesene.

The conversion of step C may be conducted in the absence of a solvent or preferably in the presence of a solvent which is preferably an aprotic organic solvent which is particularly selected from the group consisting of ethers, such as aliphatic C4-C₈-ethers, for example diethyl ether, diisopropyl ether, methyl isobutyl ether or tert-butyl methyl ether, and alicyclic C4-C₆-ethers, such as tetra hydrofuran (THF), tetra hydropyran, 2- methyltetrahydrofuran, 3-methyltetrahydrofuran or 1,4-dioxane.

In particular preferred embodiment of the invention the conversion in step C is conducted in the presence of an aprotic organic solvent that is preferably selected from alicyclic C₄- Ce-ethers, such as THF or 1,4-dioxane, and specifically is THF.

The conversion of step C is preferably effected in a pressurizable vessel, such as an autoclave. In a preferred embodiment, initially the a-farnesene preparation, the solvent, such as THF, and an ether stabilizer, such as di butyl hydroxytoluene (BHT) are charged into the vessel. After cooling the vessel to a temperature of -10 to -100°C, in particular -30 to -70°C, sulfur oxide is added in liquid form and then the reaction is conducted in the closed vessel at a temperature of about 50 to 200°C, in particular 70 to 130°C and a pressure of 2 to 20 bar, in particular 4 to 10 bar over a period of about 0.1 to 10 hours, in particular 0.5 to 3 hours. The crude product obtained after removal of the solvent can then be introduced directly into reaction step B of the process according to the invention or, for the reasons mentioned above, can be subjected to purification steps such as distillation or chromatography beforehand.

A further aspect of the present invention is directed to the use of compound I, i.e. 2,6,6- trimethyl-12-methylene-10-thiatricyclo[7.2.1.02,7]dodecane, as an aroma chemical, preferably as a fragrance. A yet further aspect of the present invention is directed to a composition comprising compound I, i.e. 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.02,7]dodecane; and at least one aroma chemical other than compound I, or at least one non-aroma chemical carrier, or both of (i) and (ii).

In a preferred embodiment of the composition of the present invention, the compound I is present in an amount in the range of > 0.001 wt.-% to < 70.0 wt.-%, more preferably in the range of > 0.01 wt.-% to < 60.0 wt.-%, particularly in the range of > 0.1 wt.-% to < 50.0 wt.-%, based on the total weight of the composition. In yet another preferred embodiment, the compound I is present in an amount in the range of 0.001 wt.-% to 10 wt.-%, more preferably 0.01 wt.-% to 5 wt.-%, yet more preferably 0.1 wt.-% to 3 wt.- %, based on the total weight of the composition. In yet another preferred embodiment, the compound I is present in an amount in the range of 20 wt.-% to 70 wt.-%, particularly 25 wt.-% to 50 wt.-%, based on the total weight of the composition.

In another preferred embodiment of the present invention, the at least one aroma chemical (i) that is included in the composition of the invention is selected from the group consisting of geranyl acetate, alpha-hexylcinnamaldehyde, 2-phenoxyethyl isobutyrate, di hydromyrcenol, methyl dihydrojasmonate , 4,6,6,7,8,8-hexamethyl-l,3,4,6,7,8-hexa- hydrocyclopenta[g]benzopyran, tetrahydrolinalool, ethyllinalool, benzyl salicylate, 2-methyl-3-(4-tert-butylphenyl)propanal, cinnamyl alcohol, 4,7-methano-3a,4,5,6,7,7a- hexahydro-5-indenyl acetate and/or 4,7-methano-3a,4,5,6,7,7a-hexahydro-6-indenyl acetate, citronellol, citronellyl acetate, tetrahydrogeraniol, vanillin, linalyl acetate, styrolyl acetate, octahydro-2, 3, 8, 8-tetramethyl-2-acetonaphthone and/or 2-acetyl-l,2,3,4,6,7,8- octahydro-2,3,8,8-tetramethylnaphthalene, hexyl salicylate, 4-tert-butylcyclohexyl acetate, 2-tert-butylcyclohexyl acetate, alpha-ionone, n-alpha-methylionone, alpha-iso- methylionone, coumarin, terpinyl acetate, 2-phenylethyl alcohol, 4-(4-hydroxy-4- methylpentyl)-3-cyclohexene-carboxaldehyde, alpha-amylcinnamaldehyde, ethylene brassylate, (E)- and/or (Z)-3-methylcyclopentadec-5-enone, 15-pentadec-ll-enolide and/or 15-pentadec-12-enolide, 15-cyclopentadecanolide, 1 -(5,6,7, 8-tetra hydro- 3,5, 5,6,8, 8-hexamethyl-2-naphthalenyl)ethanone, 2-isobutyl-4-methyltetrahydro- 2H-pyran-4-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-l-yl)-2-buten-l-ol, cis-3-hexenyl acetate, trans-3-hexenyl acetate, trans-2/cis-6-nonadienol, 2,4-dimethyl-3- cyclohexenecarboxaldehyde, 2,4,4,7-tetramethyloct-6-en-3-one, 2,6-dimethyl-5-hepten-l- al, borneol, 3-(3-isopropylphenyl)butanal, 2-methyl-3-(3,4-methylenedioxyphenyl)- propanal, 3-(4-ethylphenyl)-2,2-dimethylpropanal, 7-methyl-2H-l,5-benzodioxepin-3(4H)- one, 3, 3, 5-tri methylcyclohexyl acetate, 2,5,5-trimethyl-l,2,3,4,4a,5,6,7- octahydronaphthalen-2-ol, 3-(4-tert-butylphenyl)-propanal, ethyl 2-methylpentanoate, ethoxymethoxycyclododecane, 2,4-dimethyl-4,4a,5,9b-tetrahydroindeno[l,2- d][l,3]dioxine, (2-tert-butylcyclohexyl) acetate and 3-[5,5,6-trimethylbicyclo[2.2.1]hept- 2-yl]cyclohexan-l-ol.

In another preferred embodiment of the present invention, the at least one aroma chemical (i) is selected from the group consisting of methyl benzoate, benzyl acetate, geranyl acetate, 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, linalool, 2-isobutyl-4- methyltetrahydro-2H-pyran-4-ol and methyl benzoate.

In yet another preferred embodiment of the present invention, the at least one aroma chemical (i) is selected from the group consisting of ethylvanillin, vanillin, 2,5-dimethyl-4- hydroxy-2H-furan-3-one (furaneol) or 3-hydroxy-2-methyl-4H-pyran-4-one (maltol).

Further aroma chemicals (i) which can be combined with the compound I in the composition according to the present invention can be found, e.g., in S. Arctander, Perfume and Flavor Chemicals, Vol. I and II, Montclair, N. J., 1969, self-published or K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4th Ed., Wiley- VCH, Weinheim 2001.

Particular mention should be made in this context of: extracts from natural raw materials such as essential oils, concretes, absolutes, resins, resinoids, balsams and tinctures, such as ambergris tincture; amyris oil; angelica seed oil; angelica root oil; aniseed oil; valerian oil; basil oil; tree moss absolute; bay oil; mugwort oil; benzoin resin; bergamot oil; beeswax absolute; birch tar oil; bitter almond oil; savory oil; buchu leaf oil; cabreuva oil; cade oil; calmus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; cassia absolute; castoreum absolute; cedar leaf oil; cedar wood oil; cistus oil; citronella oil; lemon oil; copaiba balsam; copaiba balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill weed oil; dill seed oil; Eau de brouts absolute; oak moss absolute; elemi oil; tarragon oil; eucalyptus citriodora oil; eucalyptus oil; fennel oil; pine needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiacwood oil; gurjun balsam; gurjun balsam oil; helichrysum absolute; helichrysum oil; ginger oil; iris root absolute; iris root oil; jasmine absolute; calmus oil; camomile oil blue; roman chamomile oil; carrot seed oil; cascarilla oil; pine needle oil; spearmint oil; caraway oil; labdanum oil; labdanum absolute; labdanum resin; lavandin absolute; lavandin oil; lavender absolute; lavender oil; lemongrass oil; lovage oil; lime oil distilled; lime oil pressed; linalool oil; litsea cubeba oil; laurel leaf oil; mace oil; marjoram oil; mandarin oil; massoia bark oil; mimosa absolute; musk seed oil; musk tincture; clary sage oil; nutmeg oil; myrrh absolute; myrrh oil; myrtle oil; clover leaf oil; clove flower oil; neroli oil; olibanum absolute; olibanum oil; opopanax oil; orange blossom absolute; orange oil; organum oil; palmarosa oil; patchouli oil; perilla oil; peru balsam oil; parsley leaf oil; parsley seed oil; petitgrain oil; peppermint oil; pepper oil; pimento oil; pine oil; pennyroyal oil; rose absolute; rose wood oil; rose oil; rosemary oil; Dalmatian sage oil; Spanish sage oil; sandalwood oil; celery seed oil; spike-lavender oil; star anise oil; styrax oil; tagetes oil; fir needle oil; tea tree oil; turpentine oil; thyme oil; tolubalsam; tonka absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniper berry oil; wine lees oil; wormwood oil; winter green oil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil, and fractions thereof, or ingredients isolated therefrom; individual fragrances from the group of hydrocarbons, such as e.g. 3 carene; alphapinene; beta-pinene; alpha-terpinene; gamma-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-l,3,5-undecatriene; styrene; diphenylmethane; the aliphatic alcohols such as e.g. hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2- methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)-3-hexenol; 1 octen- 3-ol; mixture of 3, 4,5,6, 6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4- methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9- decenol; 10-undecenol; 4-methyl-3-decen-5-ol; the aliphatic aldehydes and acetals thereof such as e.g. hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2- dodecenal; 2,6,10-trimethyl-9-undecenal; 2,6,10 trimethyl-5,9-undecadienal; heptanal diethylacetal; l,l-dimethoxy-2,2,5 trimethyl-4-hexene; citronellyloxyacetaldehyde; (E/Z)-

1-(l-methoxypropoxy)-hex-3-ene; the aliphatic ketones and oximes thereof such as e.g.

2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3 heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one; the aliphatic sulfur-containing compounds such as e.g. 3-methylthiohexanol; 3-methyl- thiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; l-menthene-8-thiol; the aliphatic nitriles such as e.g. 2-nonenenitrile; 2-undecenenitrile; 2 tridecenenitrile; 3,12-tridecadienenitrile; 3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl-6 octenenitrile; the esters of aliphatic carboxylic acids such as e.g. (E) and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3 methyl-2- butenyl acetate; (E)-2-hexenyl acetate; (E) and (Z)-3-hexenyl acetate; octyl acetate; 3- octyl acetate; l-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E) and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2- methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octinate; methyl 2-noninate; allyl 2-isoamyloxy acetate; methyl-3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl crotonate; the acyclic terpene alcohols such as e.g. geraniol; nerol; linalool; lavandulol; nerolidol; farnesol; tetra hydrolinalool; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl- 6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2 ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-l,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7- octatrien-l-ol; and the formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2 butenoates thereof; the acyclic terpene aldehydes and ketones such as e.g. geranial; neral; citronellal; 7 hydroxy-3, 7-dimethyloctanal; 7 methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9 undecenal; geranyl acetone; as well as the dimethyl and diethylacetals of geranial, neral, 7-hydroxy-3, 7-dimethyloctanal; the cyclic terpene alcohols such as e.g. menthol; isopulegol; alpha-terpineol; terpine-4-ol; menthan-8-ol; menthan-l-ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetiverol; guajol; and the formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates thereof; the cyclic terpene aldehydes and ketones such as e.g. menthone; isomenthone; 8 mercaptomenthan-3-one; carvone; camphor; fenchone; alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethyl- ionone; alpha-irone; alpha-damascone; beta-damascone; beta-damascenone; delta- damascone; gamma-damascone; l-(2,4,4-trimethyl-2-cyclohexen-l-yl)-2-buten-l-one; l,3,4,6,7,8a-hexahydro-l,l,5,5-tetramethyl-2H-2,4a-methanonaphthalene-8(5H)-one; 2- methyl-4-(2,6,6-trimethyl-l-cyclohexen-l-yl)-2-butenal; nootkatone; dihydronootkatone;

4.6.8-megastigmatrien-3-one; alpha-sinensal; beta-sinensal; acetylated cedar wood oil (methyl cedryl ketone); the cyclic alcohols such as e.g. 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3- isocamphylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-l-ol; 2-isobutyl-4- methy I tetra hyd ro-2 H - py ra n -4-ol ; the cycloaliphatic alcohols such as e.g. alpha-3, 3-trimethylcyclohexylmethanol; 1 (4- isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-l-yl)butanol; 2- methyl-4-(2,2,3 trimethyl-3-cyclopent-l-yl)-2-buten-l-ol; 2-ethyl-4-(2,2,3-trimethyl-3 cyclopent-l-yl)-2-buten-l-ol; 3-methyl-5-(2,2,3 trimethyl-3-cyclopent-l-yl)pentan-2 ol; 3- methyl-5-(2,2,3-trimethyl-3-cyclopent-l-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3- trimethyl-3-cyclopent-l-yl)-4-penten-2-ol; l-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1- (2,2,6-trimethylcyclohexyl)hexan-3-ol; the cyclic and cycloaliphatic ethers such as e.g. cineol; cedryl methyl ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclo-dodecane; alpha- cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,l-b]furan; 3a-ethyl-6,6,9a- trimethyldodecahydro-naphtho[2,l-b]furan; l,5,9-trimethyl-13-oxabicyclo-[10.1.0]trideca-

4.8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-l-yl)-5-methyl-5-(l-methylpropyl)- 1,3-dioxane; the cyclic and macrocyclic ketones such as e.g. 4-tert-butylcyclohexanone; 2,2,5 trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclo-pentanone; 2- hydroxy-3-methyl-2-cyclopenten-l-one; 3-methyl-cis-2-penten-l-yl-2 cyclopenten-l-one; 3-methyl-2-pentyl-2-cyclopenten-l-one; 3-methyl-4-cyclopenta-decenone; 3-methyl-5- cyclopentadecenone; 3-methylcyclopentadecanone; 4-(l-ethoxyvinyl)-3, 3,5,5- tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecen-l-one; 6,7- dihydro-1, 1,2, 3, 3-pentamethyl-4(5H)-indanone; 8-cyclo-hexadecen-l-one; 7-cyclo- hexadecen-l-one; (7/8)-cyclohexadecen-l-one; 9 cyclo-heptadecen-l-one; cyclopenta- decanone; cyclohexadecanone; the cycloaliphatic aldehydes such as e.g. 2,4-dimethyl-3-cyclohexenecarbaldehyde; 2 methyl-4-(2,2,6-trimethylcyclohexen-l-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3 cyclohexene carbaldehyde; 4-(4-methyl-3-penten-l-yl)-3-cyclohexenecarbaldehyde; the cycloaliphatic ketones such as e.g. l-(3,3-dimethylcyclohexyl)-4-penten-l-one; 2,2 dimethyl-l-(2,4-dimethyl-3-cyclohexen-l-yl)-l-propanone; l-(5,5-dimethyl-l cyclo-hexen-

1-yl)-4-penten-l-one; 2,3,8,8-tetramethyl-l,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone; methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl (2,4- dimethyl-3-cyclohexen-l-yl) ketone; the esters of cyclic alcohols such as e.g. 2-tert-butylcyclohexyl acetate; 4-tert-butyl- cyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; 3,3,5- trimethylcyclohexyl acetate; decahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2, 5,5, 8a-tetramethyl-2- naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate; 4,7- methano-3a,4,5,6,7,7a-hexahydro-5 or 6 indenyl propionate; 4,7-methano-3a,4,5,6,7,7a- hexahydro-5 or 6-indenyl isobutyrate; 4,7 methanooctahydro-5 or 6-indenyl acetate; the esters of cycloaliphatic alcohols such as e.g. 1-cyclohexylethyl crotonate; the esters of cycloaliphatic carboxylic acids such as e.g. allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; cis and trans-methyl dihydrojasmonate; cis and trans-methyl jasmonate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6 dimethyl-2- cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2 cyclohexene-carboxylate; ethyl 2- methyl-l,3-dioxolane-2-acetate; the araliphatic alcohols such as e.g. benzyl alcohol; 1-phenylethyl alcohol, 2 phenylethyl alcohol, 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3- phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1 -di methyl -2 phenylethyl alcohol; l,l-dimethyl-3-phenylpropanol; l-ethyl-l-methyl-3-phenylpropanol; 2-methyl-5- phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-l-ol; 4-methoxybenzyl alcohol; l-(4-isopropylphenyl)ethanol; the esters of araliphatic alcohols and aliphatic carboxylic acids such as e.g. benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate;

2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1- phenylethyl acetate; alpha-trichloromethylbenzyl acetate; alpha, alpha-dimethyl- phenylethyl acetate; alpha, alpha-dimethylphenylethyl butyrate; cinnamyl acetate; 2- phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; the araliphatic ethers such as e.g. 2-phenylethyl methyl ether; 2 phenylethyl isoamyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydratropaaldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-l,3-dioxane; 4,4a,5,9b-tetra- hydroindeno[l,2-d]-m-dioxine; 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[l,2-d]-m dioxine; the aromatic and araliphatic aldehydes such as e.g. benzaldehyde; phenylacetaldehyde;

3-phenylpropanal; hydratropaaldehyde; 4-methylbenzaldehyde; 4 methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropyl- phenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 2-methyl-3-(4-isobutyl- phenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamaldehyde; alpha-butyl- cinnamaldehyde; alpha-amylcinnamaldehyde; alpha-hexylcinnamaldehyde; 3 methyl-5- phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3 methoxy-benzaldehyde; 4- hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxy- benzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylene- dioxyphenyl)propanal; the aromatic and araliphatic ketones such as e.g. acetophenone; 4-methylacetophenone;

4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylaceto-phenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; l-(2-naphthalenyl)-ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; l,l,2,3,3,6-hexamethyl-5-indanyl methyl ketone; 6-tert-butyl-l,l dimethyl-4 indanyl methyl ketone; l-[2,3-dihydro-l, 1,2,6- tetramethyl-3-(l-methylethyl)-lH-5 indenyl]ethanone; 5',6',7',8'-tetrahydro- 3',5',5',6',8',8'-hexamethyl-2-acetonaphthone; the aromatic and araliphatic carboxylic acids and esters thereof such as e.g. benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3- phenylglycidate; ethyl 3-methyl-3-phenylglycidate; the nitrogen-containing aromatic compounds such as e.g. 2,4,6-trinitro-l,3-dimethyl-5 tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile; 3 methyl-5-phenyl-2-pentenonitrile; 3-methyl-5-phenylpentanonitrile; methyl anthranilate; methyl-N-methylanthranilate; Schiff bases of methyl anthranilate with 7 hydroxy-3, 7- dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4 dimethyl-3-cyclo- hexenecarbaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3- phenylpropyl)pyridine; indole; skatole; 2-methoxy-3 isopropyl-pyrazine; 2-isobutyl-3- methoxypyrazine; the phenols, phenyl ethers and phenyl esters such as e.g. estragole; anethole; eugenol; eugenyl methyl ether; isoeugenol; isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether; beta-naphthyl methyl ether; beta-naphthyl ethyl ether; beta-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2 ethoxy-5- (l-propenyl)phenol; p-cresyl phenylacetate; the heterocyclic compounds such as e.g. 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2 ethyl- 4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2 ethyl-3- hydroxy-4H-pyran-4-one; the lactones such as e.g. 1,4-octanolide; 3-methyl-l,4-octanolide; 1,4-nonanolide; 1,4- decanolide; 8-decen-l, 4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5- dodecanolide; 4-methyl-l,4-decanolide; 1,15-pentadecanolide; cis and trans-ll-penta- decen-1, 15-olide; cis and trans-12-pentadecen-l, 15-olide; 1,16-hexadecanolide; 9- hexadecen-1, 16-olide; 10-oxa-l,16-hexadecanolide; ll-oxa-l,16-hexadecanolide; 12-oxa- 1,16-hexadecanolide; ethylene 1,12-dodecanedioate; ethylene 1,13-tridecanedioate; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin.

In a preferred embodiment of the present invention, the at least one non-aroma chemical carrier (ii) is selected from the group consisting of surfactants, oil components, antioxidants, deodorant-active agents and solvents.

In the context of the composition according to the present invention, a "solvent" serves for the dilution of the compound I to be used according to the invention and/or any further component of the composition without having its own aroma.

The amount of the at least one solvent is selected depending on the composition.

In yet another preferred embodiment of the present invention, the at least one solvent of the composition is selected from the group consisting of ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, triethyl citrate and isopropyl myristate.

In yet another preferred embodiment of the present invention, the at least one solvent is present in the composition in an amount of 0.01 wt.-% to 99.0 wt.-%, more preferably in an amount of 0.05 wt.-% to 95.0 wt.-%, yet more preferably in an amount of 0.1 wt.-% to 80.0 wt.-%, most preferably 0.1 wt.-% to 70.0 wt.-%, particularly in an amount of 0.1 wt.-% to 60.0 wt.-%, based on the total weight of the composition.

In yet another preferred embodiment of the present invention, the composition comprises 0.05 wt.-% to 10 wt.-%, more preferably 0.1 wt.-% to 5 wt.-%, yet more preferably 0.2 wt.-% to 3 wt.-% of at least one solvent, based on the total weight of the composition. In yet another preferred embodiment of the invention, the composition comprises 20 wt.-% to 70 wt.-%, more preferably 25 wt.-% to 50 wt.-% of at least one solvent, based on the total weight of the composition.

One embodiment of the present invention is directed to a composition comprising the compound I and at least one oil component.

In a preferred embodiment of the present invention, the at least one oil component is present in an amount of 0.1 to 80 wt.-%, more preferably 0.5 to 70 wt.-%, yet more preferably 1 to 60 wt.-%, even more preferably 1 to 50 wt.-%, particularly 1 to 40 wt.-%, more particularly 5 to 25 wt.-% and specifically 5 to 15 wt.-%, based on the total weight of the composition.

The at least one oil component may be selected, for example, from Guerbet alcohols based on fatty alcohols containing 6 to 18, preferably 8 to 10, carbon atoms and other additional esters, such as myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Also suitable are esters of Cis-Css alkyl -hydroxycarboxylic acids with linear or branched C₆-C₂2 fatty alcohols, more especially dioctyl malate, esters of linear and/or branched fatty acids with polyhydric alcohols (for example propylene glycol, dimer dial or trimer triol), triglycerides based on C₆-Cio fatty acids, liquid mono-, di- and triglyceride mixtures based on C₆-Ci8 fatty acids, esters of C₆-C₂2 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, more particularly benzoic acid, esters of dicarboxylic acids with polyols containing 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C₆-C₂2 fatty alcohol carbonates such as, for example, dicaprylyl carbonate (Cetiol® CC), Guerbet carbonates based on fatty alcohols containing 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and/or branched C₆ to C22 alcohols (for example Finsolv® TN), linear or branched, symmetrical or nonsymmetrical dialkyl ethers containing 6 to 22 carbon atoms per alkyl group such as, for example, dicaprylyl ether (Cetiol® OE), ring opening products of epoxidized fatty acid esters with polyols and hydrocarbons or mixtures thereof.

It is to be understood that the at least one antioxidant, if present, is able to inhibit or prevent undesired changes in the compositions caused by oxygen effects and other oxidative processes. The effect of the antioxidants consists in most cases in them acting as free-radical scavengers for the free radicals which arise during autoxidation.

In a preferred embodiment of the present invention, the antioxidant is selected from the group consisting of: amino acids (for example glycine, alanine, arginine, serine, threonine, histidine, tyrosine, tryptophan) and derivatives thereof, imidazoles (e.g. urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine (=[3-Alanyl-L-histidin) and derivatives thereof carotenoids, carotenes (e.g. alpha-carotene, beta-carotene, lycopene, lutein) or derivatives thereof, chlorogenic acid and derivatives thereof, lipoic acid and derivatives thereof (for example dihydrolipoic acid), a uro-th ioglucose, propylthiouracil and other thiols (for example thioredoxin, glutathione, cysteine, cystine, cystamine and the glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, gamma-linoleyl, cholesteryl and glyceryl esters thereof) and salts thereof, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), sulfoximine compounds (for example buthionine sulfoximines, homocysteine sulfoximine, buthionine sulfones, penta-, hexa-, heptathionine sulfoximine)

(metal) chelating agents (e.g. alpha-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), alpha-hydroxy acids (for example citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, boldin (= alkaloid from the plant Peumus boldus, boldo extract,

EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (e.g. gamma-linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives (for example ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (for example vitamin E acetate), vitamin A and derivatives (for example vitamin A palmitate), coniferyl benzoate of gum benzoin, rutic acid and derivatives thereof, alpha-glycosylrutin, ferulic acid, furfurylideneglucitol, butyl hydroxytoluene (BHT), butylhydroxyanisole (BHA) nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, superoxide dismutase zinc and derivatives thereof (for example ZnO, ZnSC ), selenium and derivatives thereof (for example selenomethionine) and stilbenes and derivatives thereof (e.g. stilbene oxide, trans-stilbene oxide)

In a preferred embodiment of the present invention, the anti-oxidant is selected from the group consisting of pentaerythrityl, tetra-di-tert-butyl-hydroxyhydrocinnamate, nordihydroguaiaretic acid, ferulic acid, resveratrol, propyl gallate, butyl hydroxytoluene (BHT), butylhydroxyanisole (BHA), ascorbyl palmitate and tocopherol. In yet another preferred embodiment of the present invention, the compositions according to the present invention comprise the anti-oxidant in an amount of 0.001 to 25 wt.-%, preferably 0.005 to 10 wt.-%, more preferably 0.01 to 8 wt.-%, yet more preferably 0.025 to 7 wt.-%, even more preferably 0.05 to 5 wt.-%, based on the total weight of the composition.

Deodorizing compositions (deodorants and antiperspirants) counteract, mask or eliminate body odors. Body odors are formed through the action of skin bacteria on apocrine perspiration which results in the formation of unpleasant-smelling degradation products.

One embodiment of the invention of the present invention is therefore directed to a composition comprising the compound I and at least one deodorant-active agent. In a preferred embodiment, the deodorant-active agent is selected from the groups consisting of anti-perspirants, esterase inhibitors and antibacterial agents.

Suitable antiperspirants are selected from the group consisting of salts of aluminum, zirconium or zinc. Examples are aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and complex compounds thereof, for example with 1,2-propylene glycol, aluminum hydroxyallantoinate, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and complex compounds thereof, for example with amino acids, such as glycine. Aluminum chlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and complex compounds thereof are preferably used.

In a preferred embodiment, the anti-perspirant is selected from the group consisting of aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate, aluminum hydroxyallantoinate, aluminum chloride tartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate and aluminum zirconium pentachlorohydrate.

Where perspiration is present in the underarm region, extracellular enzymes - esterases, mainly proteases and/or lipases - are formed by bacteria and split the esters present in the perspiration, releasing odors in the process. Suitable esterase inhibitors are for example trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and, in particular, triethyl citrate. Esterase inhibitors inhibit enzyme activity and thus reduce odor formation. The free acid is probably released by the cleavage of the citric acid ester and reduces the pH value of the skin to such an extent that the enzymes are inactivated by acylation. Other esterase inhibitors are sterol sulfates or phosphates such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfate or phosphate, dicarboxylic acids and esters thereof, for example glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid and malonic acid diethyl ester, hydroxycarboxylic acids and esters thereof, for example citric acid, malic acid, tartaric acid or tartaric acid diethyl ester, and zinc glycinate.

In a preferred embodiment of the present invention, the esterase inhibitor is selected from the group consisting of trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate triethyl citrate, lanosterol, cholesterol, campesterol, stigmasterol, sitosterol sulfate, sitosterol phosphate, glutaric acid, glutaric acid monoethyl ester, glutaric acid diethyl ester, adipic acid, adipic acid monoethyl ester, adipic acid diethyl ester, malonic acid, malonic acid diethyl ester, citric acid, malic acid, tartaric acid, tartaric acid diethyl ester and zinc glycinate.

The compositions according to the present invention comprises the esterase inhibitor in the range of 0.01 to 20 wt.-%, preferably 0.1 to 10 wt.-% and more particularly 0.5 to 5 wt.-%, based on the total weight of the composition.

The term "anti-bacterial agents" as used herein encompasses substances which have bactericidal and/or bacteriostatic properties. Typically these substances act against grampositive bacteria such as, for example, 4-hydroxybenzoic acid and salts and esters thereof, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)-urea, 2,4,4'-trichloro-2'- hydroxydiphenylether (triclosan), 4-chloro-3,5-dimethylphenol, 2,2'-methylene-bis-(6- bromo-4-chlorophenol), 3-methyl-4-(l-methylethyl)-phenol, 2-benzyl-4-chlorophenol, 3- (4-chlorophenoxy)-propane-l,2-diol, 3-iodo-2-propinyl butyl carbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), phenoxyethanol, glycerol monocaprate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylic acid- N-alkylamides such as, for example, salicylic acid-n-octyl amide or salicylic acid-n-decyl amide

In a preferred embodiment of the present invention, the antibacterial agent is selected from the group consisting of chitosan, phenoxyethanol, 5-chloro-2-(2,4-dichlorophenoxy)- phenol, 4-hydroxybenzoic acid and salts and esters thereof, N-(4-chlorophenyl)-N'-(3,4- dichlorophenyl)-urea, 2,4,4'-trichloro-2'-hydroxydiphenylether (triclosan), 4-chloro-3,5- dimethylphenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 3-methyl-4-(l- methylethyl)-phenol, 2-benzyl-4-chlorophenol, 3-(4-chlorophenoxy)-propane-l,2-diol, 3- iodo-2-propinyl butyl carbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), phenoxyethanol, glycerol monocaprate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylic acid-N-alkylamides.

In a preferred embodiment of the present invention, the composition comprises the antibacterial agent in the range of 0.01 to 5 wt.-% and preferably 0.1 to 2 wt.-%, based on the total weight of the composition. In a preferred embodiment of the present invention, the composition preferably comprises a surfactant. Due to the characteristic fragrance property of the compound I and its substantivity, tenacity as well as stability, it can especially be used to provide an odor, preferably a fragrance impression or aroma impression to surfactant-containing compositions such as, for example, cleaners (in particular laundry care products and allpurpose cleaners). It can preferably be used to impart a long-lasting a flowery and/or a marine and/or a green and/or a sweet note and/or a rubbery note and/or a nutty note and/or a woody note and/or a dusty note and/or a rooty note and/or a lemon note odiferous impression to a surfactant comprising composition.

In a preferred embodiment of the present invention, the compositions according to the present invention comprise at least one surfactant. The surfactant(s) are preferably selected from anionic, non-ionic, cationic, amphoteric and zwitterionic surfactants, and in particular from anionic surfactants. Surfactant-containing compositions, such as for example shower gels, foam baths, shampoos, etc., preferably contain at least one anionic surfactant.

The compositions according to the invention usually contain the surfactant(s), in the aggregate, in an amount of 0 to 40 wt.-%, preferably 0 to 20 wt.-%, more preferably 0.1 to 15 wt.-%, and particularly 0.1 to 10 wt.-%, based on the total weight of the composition. Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkyl phenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, optionally partly oxidized a lk(en)yl oligoglycosides or glucuronic acid derivatives, fatty acid-N-alkyl glucamides, protein hydrolysates (particularly wheat-based vegetable products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they may have a conventional homolog distribution, although they preferably have a narrow-range homolog distribution.

Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one COO(-) or SO₃(-) group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N- alkyl-N,N-dimethyl ammonium glycinates, for example, cocoalkyl dimethyl ammonium glycinate, N-acylaminopropyl-N,N-dimethyI ammonium glycinates, for example, cocoacyla mi nopropyl dimethyl ammonium glycinate, and 2-alkyl-3-carboxymethyl-3- hydroxyethyl imidazolines, containing 8 to 18 carbon atoms in the alkyl or acyl group, and cocoacyla mi noethyl hydroxyethyl carboxymethyl glycinate. The fatty acid amide derivative known under the CTFA name of Cocamidopropyl Betaine is particularly preferred. J

Ampholytic surfactants are also suitable, particularly as co-surfactants. Ampholytic surfactants are surface-active compounds which, in addition to a C8 to C18 alkyl or acyl group, contain at least one free amino group and at least one -COOH or -SO3H group in the molecule and which are capable of forming inner salts. Examples of suitable ampholytic surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids containing around 8 to 18 carbon atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalk-ylaminopropionate, cocoacylaminoethyl aminopropionate and acyl sarcosine.

Anionic surfactants are characterized by a water-solubilizing anionic group such as, for example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic group. Dermatologically safe anionic surfactants are known to the practitioner in large numbers from relevant textbooks and are commercially available. They are, in particular, alkyl sulfates in the form of their alkali metal, ammonium or alkanolammonium salts, alkylether sulfates, alkylether carboxylates, acyl isethionates, acyl sarcosinates, acyl taurines containing linear C12-C18 alkyl or acyl groups and sulfosuccinates and acyl glutamates in the form of their alkali metal or ammonium salts.

Particularly suitable cationic surfactants are quaternary ammonium compounds, preferably ammonium halides, more especially chlorides and bromides, such as alkyl trimethyl ammonium chlorides, dialkyl dimethyl ammonium chlorides and trialkyl methyl ammonium chlorides, for example, cetyl trimethyl ammonium chloride, stearyl trim ethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetyl methyl ammonium chloride. In addition, the readily biodegradable quaternary ester compounds, such as, for example, the dialkyl ammonium methosulfates and methyl hydroxyalkyl dialkoyloxyalkyl ammonium methosulfates marketed under the name of Stepantexe and the corresponding products of the Dehyquart® series, may be used as cationic surfactants. "Esterquats" are generally understood to be quaternized fatty acid triethanolamine ester salts. They can provide the compositions with particular softness. They are known substances which are prepared by the relevant methods of organic chemistry. Other cationic surfactants suitable for use in accordance with the invention are the quaternized protein hydrolysates.

A further aspect of the invention is directed to the use of the composition according to the invention as an aroma composition for inducing an aroma and in particular for inducing an odor or a flavor.

In one embodiment of the present invention the composition according to the invention is selected from the group consisting of perfume compositions, body care compositions (including cosmetic compositions and products for oral and dental hygiene), hygiene articles, cleaning compositions (including dishwashing compositions), textile detergent compositions, compositions for scent dispensers, foods, food supplements, pharmaceutical compositions and crop protection compositions.

Perfume compositions can be selected from fine fragrances, air fresheners in liquid form, gel-like form or a form applied to a solid carrier, aerosol sprays, scented cleaners, perfume candles and oils, such as lamp oils or oils for massage. Examples of fine fragrances are perfume extracts, Eau de Parfums, Eau de Toilettes, Eau de Colognes, Eau de Solide and Extrait Parfum.

Body care compositions include cosmetic compositions and products for oral and dental hygiene, and can be selected from after-shaves, pre-shave products, splash colognes, solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions of the oil-in-water type, of the water-in-oil type and of the water-in- oil-in-water type, such as e.g. skin creams and lotions, face creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, hair removal creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair care products such as e.g. hairsprays, hair gels, setting hair lotions, hair conditioners, hair shampoo, permanent and semi-permanent hair colorants, hair shaping compositions such as cold waves and hair smoothing compositions, hair tonics, hair creams and hair lotions, deodorants and antiperspirants such as e.g. underarm sprays, roll-ons, deodorant sticks and deodorant creams, products of decorative cosmetics such as e.g. eye-liners, eye-shadows, nail varnishes, make-ups, lipsticks and mascara, and products for oral and dental hygiene, such as toothpaste, dental floss, mouth wash, breath fresheners, dental foam, dental gels and dental strips.

Hygiene articles can be selected from joss sticks, insecticides, repellents, propellants, rust removers, perfumed freshening wipes, armpit pads, baby diapers, sanitary towels, toilet paper, cosmetic wipes, pocket tissues, dishwasher and deodorizer.

Cleaning compositions, such as e.g. cleaners for solid surfaces, can be selected from perfumed acidic, alkaline and neutral cleaners, such as e.g. floor cleaners, window cleaners, dishwashing compositions both for handwashing and machine washing use, bath and sanitary cleaners, scouring milk, solid and liquid toilet cleaners, powder and foam carpet cleaners, waxes and polishes such as furniture polishes, floor waxes, shoe creams, disinfectants, surface disinfectants and sanitary cleaners, brake cleaners, pipe cleaners, limescale removers, grill and oven cleaners, algae and moss removers, mold removers, facade cleaners.

Textile detergent compositions can be selected from liquid detergents, powder detergents, laundry pretreatments such as bleaches, soaking agents and stain removers, fabric softeners, washing soaps, washing tablets. Food means a raw, cooked, or processed edible substance, ice, beverage or ingredient used or intended for use in whole or in part for human consumption, or chewing gum, gummies, jellies, and confectionaries.

A food supplement is a product intended for ingestion that contains a dietary ingredient intended to add further nutritional value to the diet. A dietary ingredient may be one, or any combination, of the following substances: a vitamin, a mineral, an herb or other botanical, an amino acid, a dietary substance for use by people to supplement the diet by increasing the total dietary intake, a concentrate, metabolite, constituent, or extract. Food supplements may be found in many forms such as tablets, capsules, soft gels, gel caps, liquids, or powders.

Pharmaceutical compositions comprise compositions which are intended for use in the diagnosis, cure, mitigation, treatment, or prevention of disease as well as articles (other than food) intended to affect the structure or any function of the body of man or other animals.

Crop protection compositions comprise compositions which are intended for the managing of plant diseases, weeds and other pests (both vertebrate and invertebrate) that damage agricultural crops and forestry.

In a preferred embodiment of the present invention, the composition further comprises at least one auxiliary agent selected from the group consisting of preservatives, abrasives, anti-acne agents, agents to combat skin aging, anti-cellulite agents, antidandruff agents, anti-inflammatory agents, irritation-preventing agents, irritation-alleviating agents, astringents, sweat-inhibiting agents, antiseptics, anti-statics, binders, buffers, carrier materials, chelating agents, cell stimulants, care agents, hair removal agents, emulsifiers, enzymes, essential oils, fibers, film formers, fixatives, foam formers, foam stabilizers, substances for preventing foaming, foam boosters, fungicides, gelling agents, gel-forming agents, hair care agents, hair shaping agents, hair smoothing agents, moisture-donating agents, moisturizing substances, humectant substances, bleaching agents, strengthening agents, stain removal agents, optical brighteners, impregnating agents, soil repellents, friction-reducing agents, lubricants, moisturizing creams, ointments, opacifiers, plasticizers, covering agents, polish, shine agents, polymers, powders, proteins, refatting agents, exfoliating agents, silicones, skin-calming agents, skin-cleansing agents, skin care agents, skin-healing agents, skin lightening agents, skin-protective agents, skin-softening agents, cooling agents, skin-cooling agents, warming agents, skin-warming agents, stabilizers, UV-absorbent agents, UV filters, fabric softeners, suspending agents, skintanning agents, thickeners, vitamins, waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, a-hydroxy acids, polyhydroxy fatty acids, liquefiers, dyes, color-protection agents, pigments, anti -corrosives, polyols, electrolytes and silicone derivatives. A further aspect of the present invention is directed to the use of compound I, i.e. 2,6,6- trimethyl-12-methylene-10-thiatricyclo[7.2.1.02,7]dodecane, to impart an aroma impression to a composition.

Another aspect of the present invention is directed to a method of imparting an aroma impression to a composition comprising at least the step of adding the compound I to a composition, or comprising at least the step of mixing simultaneously or consecutively the compound I with the other components of said composition or with pre-formed mixtures of a part of the other components of said composition.

In one embodiment of the present invention, the impression imparted to a composition is a citrus note. In another embodiment, the impression is a woody note. In another embodiment, the impression is a fruity note. In another embodiment, the impression is a fresh note. In another embodiment, the impression is animalic note. In another embodiment, the impression is a combination of two or more of the notes selected from a citrus note, a woody note, a fruity note, a fresh note and an animalic note.

The examples below serve to illustrate the invention without adversely affecting it in any way:

EXAMPLES

Abbreviations:

BHT : 2,6-(di-tert-butyl)-4-methyl-phenol

THF: tetra hydrofuran

BF₃ x Et₂O: boron trifluoride etherate

LiAIH₄: lithium aluminum hydride

Et₂O: diethyl ether

(v/v): volume to volume

(w/w): weight to weight

Analytical methods:

HPLC method 1 (chiral separation :

Column: CHIRALPAK-IG3, 3 pm, 150 x 3 mm (2 columns in a row, from Daicel™); column temperature: 60 °C; mobile phase: water/methanol 3:7 (v/v); flow rate: 0.7 ml/min; injection volume: 1 pl; detection: 227 nm (isosbestic wavelength). HPLC method 2 (achiral separation)

Column: Zorbax Eclipse PAH 1.8 pm 50 x 4.6 mm (from Agilent®); column temperature: 60 °C; mobile phase: water/acetonitrile 8:2 (v/v) to 1:9 (v/v) in 6 min; flow rate: 1.2 ml/min; injection volume: 2 pl; detection: 210 nm.

NMR spectroscopy

^XH NMR: Bruker, 500 MHz, 297 K (25°C); ¹³C NMR: Bruker, 125 MHz, 297 K (25°C).

Example 1: Preparation of 2-r3,7-dimethylocta-2,6-dienyl1-3-methyl-2,5-dihvdro- thiophene-l.l-dioxide (Compound III) a) Synthesis:

A 35 ml microwave vial was charged with 2.0 g farnesene (ratio of a-farnesene to a- farnesene: 3:2 (w/w), 9.8 mmol), 22 mg BHT (0.12 mmol, 0.01 eq.) and 24 ml THF. The mixture was cooled to -50°C in a dry ice cooling bath and 6.3 g of liquid sulfur dioxide (98 mmol, 10 eq.) were added. The vial was capped and heated in amicrowave oven to 100°C for 1 hour at 6.2 bar. Afterwards the solvent was distilled off using a rotary evaporator at a temperature of 20°C to obtain 2.3 g of a yellow oil. b Purification

The obtained oil was dissolved in 10 ml dichloromethane, 5 g Celite 503 (from Macherey- Nagel) were added, and the solvent was distilled off using a rotary evaporator at a temperature of 20°C. In the thus obtained form as coated on kieselguhr particles the crude product is transferred to and purified by preparative reversed-phase HPLC (Combiflash, H₂O/ACN = 9: 1 (v/v) to 1:9 (v/v) in 10 min, then constant 1:9 (v/v) for 25 min, flow rate: 75 ml/min, column: RediSep C18, 130 g, RS120 C18ec, detection: 200 nm). The obtained fractions 33 and 34 (at retention times of about 11 to 12 min) were combined and extracted with 100 ml dichloromethane. The organic phase was dried and the solvent was distilled off using a rotary evaporator at a temperature of 20°C to give 480 mg of a mixture of compound III (2-[3,7-dimethylocta-2,6-dienyl]-3-methyl-2,5- di hydrothiophene 1,1-dioxide) and compound IV (3-[4,8-dimethylnona-3,7-dienyl]-2,5- di hydrothiophene 1,1-dioxide) as a dark yellow liquid.

Analysis of the obtained product by HPLC method 1: R/S-(2Z)-2-r3,7-dimethylocta-2,6-dienyl1-3-methyl-2,5-dihvdrothiophene 1,1-dioxide: Peaks at 11.23 min (16.7 area%) and 12.28 min (16.0 area%)

R/S-(2E)-2-r3,7-dimethylocta-2,6-dienyll-3-methyl-2,5-dihvdrothioohene 1,1- dioxide:

Peaks at 18.24 min (approx. 19.3 area%) and 20.40 min (19.3 area%) 3-r(3E/Z)-4,8-dimethylnona-3,7-dienyl1-2,5-dihvdrothioDhene 1,1-dioxide:

Peaks at 13.34 min (11.3 area%) and 18.24 min (approx. 11.3 area%). Example 2: Preparation of 2-r3,7-dimethylocta-2,6-dienyl1-3-methyl-2,5-dihvdro- thiophene-l.l-dioxide (Compound a) Synthesis:

A 35 ml microwave vial was charged with 2.0 g farnesene (ratio of a-farnesene to a- farnesene: 3:2 (w/w), 9.8 mmol), 22 mg BHT (0.12 mmol, 0.01 eq.) and 24 ml THF. The mixture was cooled to -50°C in a dry ice cooling bath and 6.3 g of liquid sulfur dioxide (98 mmol, 10 eq.) were added. The vial was capped and heated in a microwave oven to 100°C for 1 hour at 6.2 bar. Afterwards the solvent was distilled off using a rotary evaporator at a temperature of 20°C to obtain 2.5 g of a yellow oil. b Purification

The obtained oil was dissolved in 10 ml dichloromethane, 5 g Celite 503 (from Macherey- Nagel) were added, and the solvent was distilled off using a rotary evaporator at a temperature of 20°C. In the thus obtained form as coated on kieselguhr particles the crude product is transferred to and purified by preparative reversed-phase HPLC (Combiflash, H₂O/ACN = 9: 1 (v/v) to 1:9 (v/v) in 10 min, then constant 1:9 (v/v) for 25 min, flow rate: 75 ml/min, column: RediSep C18, 130 g, RS120 C18ec, detection: 200 nm). The obtained fractions 33, 34 and 35 (at retention times of about 11 to 12 min) were combined and extracted with 100 ml dichloromethane. The organic phase was dried and the solvent was distilled off using a rotary evaporator at a temperature of 20°C to give 630 mg of a mixture of compound III (2-[3,7-dimethylocta-2,6-dienyl]-3-methyl-2,5- di hydrothiophene 1,1-dioxide) and compound IV (3-[4,8-dimethylnona-3,7-dienyl]-2,5- di hydrothiophene 1,1-dioxide) as a dark yellow liquid.

Analysis of the obtained product by HPLC method 1: R/S-(2Z)-2-r3,7-dimethylocta-2,6-dienyl1-3-methyl-2,5-dihvdrothiophene 1,1-dioxide: Peaks at 11.23 min (17.0 area%) and 12.28 min (15.8 area%)

R/S-(2E)-2-r3,7-dimethylocta-2,6-dienyll-3-methyl-2,5-dihvdrothioohene 1,1- dioxide:

Peaks at 18.24 min (approx. 18.5 area%) and 20.40 min (18.5 area%) 3-r(3E/Z)-4,8-dimethylnona-3,7-dienyl1-2,5-dihvdrothioDhene 1,1-dioxide:

Peaks at 13.34 min (10.7 area%) and 18.24 min (approx. 10.7 area%).

Example 3: Preparation of 2,6,6-trimethyl-12-methylene-10A⁶-thiatricvclor7.2.1.0²'⁷ldo- decane-10,10-dioxide (Compound II) a) Synthesis:

480 mg 2-[3,7-dimethylocta-2,6-dienyl]-3-methyl-2,5-dihydrothiophene 1,1-dioxide (1.8 mmol, compound III) obtained in Example 1 were dissolved in 10 ml acetonitrile and 508 mg BF₃ x Et₂O (3.6 mmol, 2 eq.) were added. The reaction mixture was stirred for 3 hours at room temperature. After removal of the solvent under vacuum at 20°C 800 mg of a brown solid were obtained. b) Purification The obtained brown solid was dissolved in 10 ml dichloromethane, 3 g Celite 503 (from Macherey-Nagel) were added, and the solvent was distilled off using a rotary evaporator at a temperature of 20°C. In the thus obtained form as coated on kieselguhr particles the crude product is transferred to and purified by preparative reversed-phase HPLC (Combiflash, H₂O/ACN = 9: 1 (v/v) to 1:9 (v/v) in 10 min, then constant 1:9 (v/v) for 10 min, flow rate: 75 ml/min, column: RediSep C18, 130 g, RS120 C18ec, detection: 200 nm). The obtained fractions 25, 26 and 27 (at retention times of about 10.5 to 11.5 min) were combined and extracted with 100 ml dichloromethane. The organic phase was dried and the solvent was distilled off using a rotary evaporator at a temperature of 20°C to give 150 mg of compound II (2,6,6-trimethyl-12-methylene-10A⁶-thiatricyclo[7.2.1.0²'⁷]do- decane-10,10-dioxide) as a white solid (mp. 140°C).

Analysis of the obtained product by HPLC method 1:

2.6.6-Trimethyl-12-methylene-10A⁶-thiatricvclor7.2.1.0²'⁷ldodecane-10.10-dioxide: Peaks at 10.36 min (48.4 area%), 13.13 min (9.1 area%) and 18.67 min (40.9 area%).

Example 4: Preparation of 2,6.6-trimethyl-12-methylene-10A⁶-thiatricvclor7.2.1.0²'⁷ldo- decane-lO.lO-dioxide (Compound II) a) Synthesis:

630 mg 2-[3,7-dimethylocta-2,6-dienyl]-3-methyl-2,5-dihydrothiophene 1,1-dioxide (2.5 mmol, compound III) obtained in Example 2 were dissolved in 10 ml acetonitrile and 719 mg BF₃ x Et₂O (5 mmol, 2 eq.) were added. The reaction mixture was stirred for 3 hours at room temperature. After removal of the solvent under vacuum at 20°C 1130 mg of a brown solid were obtained. b) Purification

The obtained brown solid was dissolved in 10 ml dichloromethane, 3 g Celite 503 (from Macherey-Nagel) were added, and the solvent was distilled off using a rotary evaporator at a temperature of 20 °C. In the thus obtained form as coated on kieselguhr particles the crude product is transferred to and purified by preparative reversed-phase HPLC (Combiflash, H₂O/ACN = 9: 1 (v/v) to 1:9 (v/v) in 10 min, then constant 1:9 (v/v) for 10 min, flow rate: 75 ml/min, column: RediSep C18, 130 g, RS120 C18ec, detection: 200 nm). The obtained fractions 20, 21 and 22 (at retention times of about 10.5 to 11.5 min) were combined and extracted with 100 ml dichloromethane. The organic phase was dried and the solvent was distilled off using a rotary evaporator at a temperature of 20 °C to give 242 mg of compound II as a white solid which according to NMR analysis was a 85: 15 mixture of two diastereomers of compound II (2,6,6-trimethyl-12-methylene-10A⁶- thiatricyclo[7.2.1.0²'⁷]dodecane-10,10-dioxide).

Analysis of the obtained product by HPLC method 1:

2.6.6-Trimethyl-12-methylene-10A⁶-thiatricvclor7.2.1.0²'⁷ldodecane-10,10-dioxide: Peaks at 10.36 min (46.0 area%), 13.15 min (11.8 area%) and 18.62 min (40.4 area%). NMR-Characterization of two diastereomers:

Major diastereomer: ¹H-NMR (500 MHz, CDCh, TMS) 5 (ppm) = 5.19 (d, J = 22.7 Hz, 2H), 3.52 (m, 1H), 3.34 (d, J = 13.4 Hz, 1H), 3.17 (ddd, J = 13.4, 8.0, 1.0 Hz, 1H), 2.50 (d, J = 8.3 Hz, 1H), 2.21 (d, J = 13.5 Hz, 1H), 1.85 - 1.79 (m, 1H), 1.79 - 1.64 (m, 2H), 1.53 (m, 1H), 1.47 ( m,lH), 1.36 - 1.13 (m, 3H), 0.99 (s, 3H), 0.93 (s, 3H), 0.84 (s, 3H).

¹³C-NMR (125 MHz, CDCh, TMS): 5 (ppm) = Cl: 56.35 (d), C2: 36.87 (s), C3: 34.40 (t), C4: 19.04 (t), C5: 41.75 (t), C6: 33.05 (s), C7: 43.68 (d), C8: 26.30 (t), C9: 63.98 (d), Cll: 57.41 (t), C12: 142.67 (s), C13: 113.26(t), C14: 21.26 (q), C15: 32.51 (q), C16: 20.90 (q).

Minor diastereomer: ¹H-NMR (500 MHz, CDCh, TMS) 5 (ppm) = 5.19 (d, J = 22.7 Hz, 2H), 3.50 - 3.46 (m, 1H), 3.37 (d, J = 13.5 Hz, 1H), 3.27 (ddd, J = 13.5, 8.3, 1. Hz, 1H), 2.52 ( d, J = 7.5 Hz, 1H), 2.21 (d, J = 13.5 Hz, 1H), 1.88 - 1.18 (m, 8H), 1.16 (s, 3H) l.ll(s, 3H) 0.86 (s, 3H). ¹³C-NMR (125 MHz, CDCh, TMS): 5 (ppm) = Cl: 57.78(d), C2: 39.08(s), C3: 31.27(t), C4: 18.96(q), C5: 33.85(t), C6: 33.69(s), C7: 43.34(d), C8: 29.62(t), C9: 63.56(d), Cll: 57.08(t), C12: 142.34(s), C13: 113.33(f), C14: 28.60(q), C15: 31.52(q), C16: 30.24(q).

Example 5: Preparation of 2,6,6-trimethyl-12-methylene-10-thiatricvclor7.2.1.0²'⁷1do- decane (Compound I) a) Synthesis:

A three-necked round-bottom flask was charged with 308 mg LiAIH₄ (8.1 mmol, 15 eq.) and 20 ml EtzO. The suspension was cooled to 3 °C and a solution of 145 mg 2,6,6- trimethyl-12-methylene-10A⁶-thiatricyclo[7.2.1.0²'⁷]dodecane-10,10-dioxide (0.54 mmol, compound II, from Example 3) in 10 ml EtzO was slowly added. The reaction mixture was heated to reflux for 5 hours and then cooled to 3°C. 2.6 g of NazSCh x 10 H₂O were added and the mixture was stirred at this temperature until hydrogen formation ceased after about 2 hours. Following filtration the filtercake was washed twice with 20 ml dichloromethane each. The combined filtrates were evaporated at a temperature of 20°C to obtain 114 mg 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'^7]dodecane (compound I) as a beige solid. b) Purification

The obtained beige solid was dissolved in 10 ml dichloromethane, 3 g Celite 503 (from Macherey-Nagel) were added, and the solvent was distilled off using a rotary evaporator at a temperature of 20°C. In the thus obtained form as coated on kieselguhr particles the crude product is transferred to and purified by preparative reversed-phase HPLC (Combiflash, HzO/ACN = 90: 10 (v/v) to 5:95 (v/v) in 10 min, then constant 5:95 (v/v) for 10 min, flow rate: 40 ml/min, column: RediSep C18, 43 g, RS120 C18ec, detection: 200 nm). The obtained fractions 26 to 29 (at retention times of about 13 to 14 min) were combined and extracted with 100 ml dichloromethane. The organic phase was dried and the solvent was distilled off using a rotary evaporator at a temperature of 20°C to give 15.5 mg of compound I as a colorless liquid which according to NMR analysis was a 82: 18 mixture of two diastereomers of compound I (2,6,6-trimethyl-12-methylene-10- thiatricyclo[7.2.1.0²'⁷]dodecane).

Analysis of the obtained product by HPLC method 2:

2,6.6-trimethyl-12-methylene-10-thiatricvclor7.2.1.0²'⁷ldodecane:

Peak at 5.28 min (93.3 area%).

NMR-Characterization of two diastereomers:

Major diastereomer:

¹H-NMR (500 MHz, CDCh, TMS) 5 (ppm) = 4.65 (d, J = 124.8 Hz, 2H), 3.75 (t, J = 2.5 Hz, 1H), 2.94 (d, J = 10.6 Hz, 1H),2.7O (dd, J = 10.6, 6.6 Hz, 1H), 2.10 (d, J = 6.6 Hz, 1H), 1.82 - 1.60 (m, 4H), 1.47 (m, 3H), 1.29 - 1.20 (m, 1H), 1.05 (dd, J = 13.5, 3.2 Hz, 1H), 0.91 (s, 3H), 0.86 (s, 3H), 0.81 (s, 3H).

¹³C-NMR (125 MHz, CDCh, TMS): 5 (ppm) = Cl: 56.14 (d), C2: 36.43 (s), C3: 33.15 (t), C4: 19.27 (t), C5: 42.20 (t), C6: 32.64 (s), C7: 44.05 (d), C8: 32.85 (t), C9: 49.32 (d), Cll: 28.57 (t), C12: 152.11 (s), C13: 102.07 (t), C14: 21.28 (q), C15: 33.15 (q), C16: 22.17 (q).

Minor diastereomer: ¹H-NMR (500 MHz, CDCh, TMS) 5 (ppm) = 4.65 (d, J = 124.8 Hz, 2H), 3.69 (m, 1H), 3.02 (d, J = 10.4 Hz, 1H), 2.78 (dd, J = 10.5, 6.5 Hz, 1H), 2.13 (d, J = 6,60 Hz, 1H), 1.83 - 1.60 (m, 5H), 1.47 (m, 3H), 1.16 (s, 4H), 1.10 (s, 3H), 0.79 (s, 3H).

¹³C-NMR (125 MHz, CDCh, TMS): 5 (ppm) = Cl: 57.78(d), C2: 39.08(s), C3: 31.27(t), C4: 18.96(q), C5: 33.85(t), C6: 33.69(s), C7: 43.34(d), C8: 29.62(t), C9: 63.56(d), Cll: 57.08(t), C12: 142.34(s), C13: 113.33(f), C14: 28.60(q), C15: 31.52(q), C16: 30.24(q).

Example 6: Preparation of 2,6.6-trimethyl-12-methylene-10-thiatricvclor7.2.1.0²'⁷ldo- decane (Compound I) a) Synthesis:

A three-necked round-bottom flask was charged with 500 mg LiAIH₄ (13 mmol, 15 eq.) and 20 ml EtzO. The suspension was cooled to 3°C and a solution of 237 mg 2,6,6- trimethyl-12-methylene-10A⁶-thiatricyclo[7.2.1.0²'⁷]dodecane-10,10-dioxide (0.88 mmol, compound II, from Example 3) in 10 ml EtzO was slowly added. The reaction mixture was heated to reflux for 5 hours and then cooled to 3°C. 4.2 g of NazSCh x 10 H₂O were added and the mixture was stirred at this temperature until hydrogen formation ceased after about 2 hours. Following filtration the filtercake was washed twice with 20 ml dichloromethane each. The combined filtrates were evaporated at a temperature of 20°C to obtain 135 mg 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'^7]dodecane (compound I) as a beige solid. b) Purification

The obtained beige solid was dissolved in 10 ml dichloromethane, 3 g Celite 503 (from Macherey-Nagel) were added, and the solvent was distilled off using a rotary evaporator at a temperature of 20 °C. In the thus obtained form as coated on kieselguhr particles the crude product is transferred to and purified by preparative reversed-phase HPLC (Combiflash, H₂O/ACN = 90: 10 (v/v) to 5:95 (v/v) in 10 min, then constant 5:95 (v/v) for 10 min, flow rate: 40 ml/min, column: RediSep C18, 43 g, RS120 C18ec, detection: 200 nm). The obtained fractions 20 to 22 (at retention times of about 13.5 to 14.5 min) were combined and extracted with 100 ml dichloromethane. The organic phase was dried and the solvent was distilled off using a rotary evaporator at a temperature of 20°C to give 66.6 mg of compound I (2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]do- decane) as a colorless liquid.

Analysis of the obtained product by HPLC method 2:

2,6.6-trimethyl-12-methylene-10-thiatricvclor7.2.1.0²'⁷ldodecane:

Peak at 5.27 min (92.1 area%).

Example 7: Combining 2,6.6-trimethyl-12-methylene-10-thiatricvclor7.2.1.0²'⁷ldodecane (Compound I) of Examples 5 and 6

The products of examples 9 and 10 were dissolved and rinsed with trichloromethane and combined. The solvent was distilled off at 20 °C using a rotary evaporator. The residue was then dissolved in 5 ml absolute ethanol and the solvent was distilled off at 20°C with a rotary evaporator to obtain 79 mg 2,6,6-trimethyl-12-methylene-10- thiatricyclo[7.2.1.0²'⁷]dodecane (0.3 mmol, compound I) as a colorless liquid.

Analysis of the obtained product by HPLC method 2:

2,6.6-trimethyl-12-methylene-10-thiatricvclor7.2.1.0²'⁷ldodecane:

Peak at 5.27 min (100.0 area%).

Combined yields of Examples 1 and 2 (sulfonylation step). Examples 3 and 4 (cyclization step) and Examples 5, 6 and 7 (reduction step):

Sulfonylation: 1110 mg yield of compound III (21%)

Cyclization: 392 mg yield of compound II (7% over 2 steps) Reduction: 79 mg yield of compound I (2% over 3 steps)

Example 8: Olfactory evaluation of compound I

In order to test the quality and intensity of the compounds of the present invention and the mixtures, scent strip tests were performed.

For this purpose, strips of absorbent paper were dipped into a solution containing 1 to 10 wt.% of the compound (mixture) to be tested in triethyl citrate. After formation of a gas phase equilibrium (about 30 s) the scent impression was olfactively evaluated by a panel of trained experts. The odor impression is described in the following table 1: Table 1:

Intensity: 5

Claims

Claims

1. The compound 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane.

2. The compound 2,6,6-trimethyl-12-methylene-10A⁶-thiatricyclo[7.2.1.0²'⁷]dodecane- 10,10-dioxide.

3. A process for the preparation of 2,6,6-trimethyl-12-methylene-10- thiatricyclo[7.2.1.0²'⁷]dodecane which comprises reacting 2,6,6-trimethyl-12- methylene-10A⁶-thiatricyclo[7.2.1.0²'⁷]dodecane-10,10-dioxide with a reducing agent.

4. The process of claim 3 where the reducing agent is a complex hydride.

5. The process of claim 4, where the reducing agent is an aluminum hydride, in particular lithium aluminum hydride.

6. The process of any one of claims 3 to 5 which additionally comprises the provision of 2,6,6-trimethyl-12-methylene-10A⁶-thiatricyclo[7.2.1.0²'⁷]dodecane 10,10 dioxide by a process comprising the treatment of 2-[3,7-dimethylocta-2,6-dienyl]-3-methyl- 2,5-dihydrothiophene-l,l-dioxide with an acid.

7. The process of claim 7, where the acid comprises or is a Broensted acid.

8. The process of claim 7, where the acid comprises or is a Lewis acid.

9. The process of claim 8, where the acid is boron trifluoride or a complex of boron trifluouride with an ether.

10. The process of any one of claims 3 to 5 which additionally comprises the provision of 2-[3,7-dimethylocta-2,6-dienyl]-3-methyl-2,5-dihydrothiophene-l,l-dioxide by a process comprising the reaction of a-farnesene with sulfur dioxide.

11. The use of 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane as an aroma chemical.

12. A composition comprising 2,6,6-trimethyl-12-methylene-10- thiatricyclo[7.2.1.0²'⁷]dodecane and

(i) at least one aroma chemical other than 2,6,6-trimethyl-12-methylene-10- thiatricyclo[7.2.1.0²'⁷]dodecane, or

(ii) at least one non-aroma chemical carrier, or

(iii) both of (i) and (ii).

13. Use of 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane to impart an aroma note to a composition.

14. A method of imparting an aroma note to a composition comprising at least the step of adding 2,6,6-trimethyl-12-methylene-10-thiatricyclo[7.2.1.0²'⁷]dodecane to a composition.

15. The use or method according to claim 13 or 14, wherein the aroma note is selected from the group consisting of a citrus note, a woody note, a fruity note, a fresh note and an animalic note or a combination thereof.