Substituted 4-methylene-tetrahydropyrans, 4-methyl-dihydropyrans and 4-methyl-tetrahydropyrans and their use as aroma chemicals

Abstract

The present invention relates to a compound of formula (I): [Formula 1] TIFF2023505732000074.tif31164, where the variables are as defined in the claims and specification. and substituted 4-methylene-tetrahydropyrans, 4-methyl-dihydropyrans and 4-methyl-tetrahydropyrans of the formula (I), their stereoisomers, mixtures of stereoisomers thereof, mixtures of different di- and tetrahydropyrans (I), and mixtures comprising at least one di- or tetrahydropyran (I) and at least one cyclic acetal which is a 1,3-dioxane having an isobutanol-2-yl (derived) substituent in the 2-position and two methyl substituents in the 4,4- or 5,5-positions. The invention also relates to the use of such compounds as aroma chemicals and / or for modifying and / or enhancing the aroma of compositions, compositions comprising such compounds, processes for preparing such compounds, and products obtainable by these processes.

Description

[Technical field]

[0001] The present invention relates to substituted 4-methylene-tetrahydropyrans, 4-methyl-dihydropyrans and 4-methyl-tetrahydropyrans of formula (I) having an isobutanol-2-yl (derived) substituent in the ortho position relative to the ring oxygen atom, as defined below, their stereoisomers, mixtures of their stereoisomers, mixtures of different di- and tetrahydropyrans (I) and mixtures comprising at least one di- or tetrahydropyran (I) and at least one cyclic acetal which is a 1,3-dioxane having an isobutanol-2-yl (derived) substituent in the 2-position and two methyl substituents in the 4,4- or 5,5-positions. The present invention also relates to the use of such compounds as aroma chemicals and / or for modifying and / or enhancing the aroma of a composition, compositions comprising such compounds, processes for preparing such compounds and products obtainable by these processes. [Background technology]

[0002] Aroma chemicals, especially fragrances, are of great interest, especially in the field of cosmetic compositions and cleaning and laundry compositions.Fragrances of natural origin are mostly expensive, often have limited availability, and are also susceptible to changes in content, purity, etc. due to variations in environmental conditions.Therefore, in order to avoid these undesirable factors, there is great interest in creating synthetic materials that have sensory properties similar to those of more expensive natural fragrances or that have novel and interesting sensory profiles.

[0003] Although a large number of aroma chemicals already exist, new ingredients are constantly needed to be able to meet the numerous properties desired for a wide variety of application areas.These primarily include sensory properties, i.e. the compounds should have advantageous odor (olfactory) or taste properties.Aroma chemicals should also have additional favorable secondary properties, such as efficient preparation methods, the possibility of providing a better sensory profile as a result of synergistic effects with other aroma chemicals, higher stability, higher scalability and / or better staying power in a wide range of compositions and under specific application conditions, etc.

[0004] However, the search for targeted substances with specific sensory properties (e.g., a specific odor) is extremely difficult, since even small changes in chemical structure can result in large changes in sensory properties such as odor and also taste. Thus, the search for new fragrances and flavors is often difficult, time-consuming, and laborious, and it is unclear whether a substance with the desired odor and / or taste will actually be found.

[0005] EP-A-1493737 describes the preparation of 4-methylenetetrahydropyrans, or their double bond isomers 4-methyldihydropyrans, which are said to be useful synthetic intermediates for perfumes, pharmaceuticals or agrochemicals, and which have an alkyl, alkenyl, optionally substituted cycloalkyl or optionally substituted aryl group in the ortho position relative to the ring oxygen atom.

[0006] US 2014 / 0107352 describes such compounds as intermediates in the synthesis of 4-methyltetrahydropyran. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] EP-A-1493737 [Patent Document 2] US 2014 / 0107352 Summary of the Invention [Problem to be solved by the invention]

[0008] The aim of the present invention was to provide new aroma chemicals. Furthermore, there is a need for strong-smelling substances that can be used in aroma compositions. In addition, these substances should be capable of being combined with other aroma chemicals, allowing the creation of new and advantageous sensory profiles. Furthermore, the process of preparation of these new aroma chemicals should be easy and efficient, allowing their rapid, economical and environmentally friendly production. [Means for solving the problem]

[0009] These and further objects are achieved by a compound of formula (I), or a mixture thereof [i.e. a mixture of different compounds (I), more precisely a mixture of two or more different compounds (I)], or a stereoisomer thereof, or a mixture with the corresponding cyclic acetal (1,3-dioxane), as shown below.

[0010] The present invention relates to a compound represented by general formula (I):

[0011] [ka] (In the formula, R 1 , R 2 , R 3 and R 4 is hydrogen; or R 2 , R 3 or R 4 One of them is R 1 Together with represents a double bond; R 2 , R 3 or R 4 all of the remainder are hydrogen; R 5 is hydrogen, C1-C4-alkyl and -C(=O)-R 6 wherein R 6 is selected from the group consisting of hydrogen and C1-C4-alkyl or a stereoisomer thereof, or a mixture of stereoisomers thereof, or a mixture of different compounds (I); Alternatively, at least one compound of formula (I) and a compound of formula (II.1) and / or (II.2):

[0012] [ka] (In the formula, R 5 is as defined above) The present invention relates to a mixture of one or both of the compounds of the formula (I).

[0013] Another aspect of the present invention relates to the use of a compound of formula (I), of a stereoisomer thereof, of a mixture of stereoisomers thereof, of a mixture of different compounds (I), or of a mixture of at least one compound of formula (I) with one or both of the compounds of formulae (II.1) and / or (II.2) as aroma chemicals.

[0014] The present invention also relates to the use of a compound of formula (I) as defined above, a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I) or a mixture of at least one compound of formula (I) with one or both of the compounds of formulae (II.1) and / or (II.2), for modifying and / or enhancing the aroma of a composition; in particular for modifying and / or enhancing the fragrance impression of a composition; especially for modifying the odor characteristics of a fragranced ready-to-use composition.

[0015] The present invention further relates to a method for preparing an aromachemical composition, in particular a fragranced composition, especially a fragranced ready-to-use composition, comprising incorporating in a composition, in particular a ready-to-use composition, at least one compound of formula (I), its stereoisomer or a mixture of its stereoisomers, optionally mixed with one or both of the compounds of formula (II.1) and / or (II.2).

[0016] The present invention further relates to a method for modifying and / or enhancing the aroma of a composition, comprising incorporating into a composition, in particular a ready-to-use composition, at least one compound of formula (I), its stereoisomer or a mixture of its stereoisomers, optionally mixed with one or both of the compounds of formula (II.1) and / or (II.2); preferably a method for modifying and / or enhancing the fragrance impression of a composition; in particular a method for modifying the odor characteristics of a perfuming composition, in particular of a fragranced composition, especially of a fragranced ready-to-use composition.

[0017] In another aspect, the present invention relates to a composition comprising a compound of formula (I), or a stereoisomer thereof, or a mixture of two or more stereoisomers thereof, or a mixture of two or more different compounds of formula (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one further ingredient selected from the group consisting of fragrance chemicals, non-fragrance chemical carriers, antioxidants and deodorising actives.

[0018] Another aspect of the invention is a process for preparing a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), comprising reacting isoprenol with hydroxypivalinaldehyde in an acidic medium to give R 5 is H and R 2 , R 3 or R 4 One of them is R 1 Together with represents a double bond, while R 2 , R 3 or R 4 and, if desired, etherifying or esterifying this compound to obtain a reaction mixture containing compound (I) in which all of the remainder of R are hydrogen. 5 obtaining a compound (I) in which R is different from H. 1 , R 2 , R3 and R 4 To obtain a compound where R is hydrogen, 2 , R 3 or R 4 One of them is R 1 Together with represents a double bond, while R 2 , R 3 or R 4 The compound in which the remainder is all hydrogen is subjected to a hydrogenation reaction either before or after the etherification or esterification reaction.

[0019] Yet another aspect of the present invention is a compound of formula (I), 5 is different from hydrogen), its stereoisomer, its mixture of stereoisomers or a mixture of different compounds (I), comprising subjecting hydroxypivalinaldehyde to an etherification or esterification reaction, and reacting the etherification or esterification product with isoprenol under BF3 catalysis to obtain R 5 is C1-C4-alkyl or -C(=O)-R 6 and R 2 , R 3 or R 4 One of them is R 1 Together with represents a double bond, while R 2 , R 3 or R 4 and obtaining a product in which the remainder of R is all hydrogen. 1 , R 2 , R 3 and R 4 To obtain a compound where R is hydrogen, 2 , R 3 or R 4 One of them is R 1 Together with represents a double bond, while R 2 , R 3 or R 4 The compound in which the remainder is all hydrogen is subjected to a hydrogenation reaction.

[0020] Finally, the present invention relates to the products obtainable by said preparation process. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Definition: In the context of the present invention, the term "aroma" refers to sensory properties and includes smell and / or flavor.

[0022] The term "aroma chemicals" refers to substances used to obtain an aroma impression (the term "aroma impression" is used interchangeably herein with the term "note"), including its use to obtain an olfactory impression and / or a flavor impression. The term "olfactory impression" or "odor impression" refers to an odor impression that is not accompanied by either a positive or negative judgment, whereas the term "scent impression" or "fragrance impression" as used herein (used interchangeably herein) is associated with an odor impression that is generally perceived as pleasant. Thus, "fragrance" or "aroma" refers to aroma chemicals that induce a primarily pleasant odor impression. Flavor refers to aroma chemicals that induce a taste impression.

[0023] The term "aroma profile" refers to the overall aroma impression of an aroma chemical, which is made up of the individual aroma impressions of the aroma chemicals.

[0024] The term "fragrance composition" as used herein refers to a composition that induces an aroma. The term fragrance composition includes "odor composition" and / or "flavor composition." An odor composition is a composition that primarily induces an odor impression, whereas a flavor composition is a composition that primarily induces a taste impression.

[0025] The term "odor composition" includes "fragrance composition" or "scent composition" (used interchangeably herein), which primarily induces an odor impression that is generally perceived as pleasant.

[0026] "Pleasant odor", "pleasant odor impression", "pleasant fragrance characteristics", "perceived pleasant odor impression" and similar terms are hedonic expressions describing the niceness and conciseness of the odor impression conveyed by aroma chemicals. The more general hedonic expressions "advantageous sensory characteristics" or "advantageous organoleptic characteristics" describe the niceness and conciseness of the sensory impression conveyed by aroma chemicals. In the context of the present invention, the terms "sensory" and "sensation" relate to olfactory or flavor characteristics. "Pleasantness" and "simplicity" are terms well known to perfumers skilled in the art. "Pleasantness" generally refers to a pleasant sensory impression that is positively perceived, which is brought about in nature. However, "pleasant" is not necessarily synonymous with "sweet". "Pleasant" may also be a musk or sandalwood odor. "Simplicity" generally refers to a naturally occurring sensory impression that reproducibly reminds the same particular thing to the same test panel. For example, a substance may have an odor that naturally reminds one of an "apple". This odor would then simply be that of "apple". If this apple odor was very pleasant, for example because it reminded one of a sweet, ripe apple, then the odor would be called "pleasant". However, a typical sour apple odor may also be simple. If both reactions occur when smelling the substance, thus giving a pleasant simple apple odor in this example, then the substance has particularly advantageous sensory properties.

[0027] The term "strong-smelling substance" refers to a substance or aroma chemical that exhibits a strong odor impression. Strong odor impression is to be understood as meaning the property of an aroma chemical that allows an impressive perception even at very low gas space concentrations.

[0028] The intensity can be determined by threshold measurements. The threshold is the concentration of a substance in the relevant gas space at which an odor impression can still only be perceived by a representative test panel, but this does not have to be defined any more. Probably belonging to the most odoriferous known substance class (i.e. having a very low odor threshold) are the thiols, whose threshold is often measured in ppb / m 3 is within the range.

[0029] The term "tenacity" describes the evaporation behavior of a fragrance chemical over time. Tenacity can be determined, for example, by applying the fragrance chemical to a test paper and then olfactory evaluating the odor impression of the test paper. For fragrance chemicals with high tenacity, there is a long period after which the panel can still identify the fragrance impression.

[0030] The term "substantivity" describes the interaction of fragrance chemicals with a surface, such as skin or fabric, especially after subsequent treatment of the surface, such as washing. This substantivity can be determined by washing fabrics with a fabric detergent composition containing fragrance chemicals, followed by olfactory evaluation of the fabrics (wet fabrics) immediately after washing, as well as evaluation of dry fabrics after extended storage.

[0031] The term "stability" describes the behavior of a fragrance chemical when in contact with oxygen, light and / or other substances. A fragrance chemical with high stability preferably maintains its fragrance profile over an extended period of time in a wide variety of compositions and under a variety of storage conditions.

[0032] In order to impart a long-lasting fragrance impression to the composition, or to surfaces treated with the composition, the retention, substantivity and stability of the fragrance chemicals in the composition should preferably be high.

[0033] The terms "booster", "boosting" or "boost" are used herein to describe the effect of enhancing and / or modifying the aroma of an aroma chemical or the aroma of a composition. The term "enhancing" includes increasing the pleasantness and / or clarity of the aroma and / or increasing the intensity. The term "modifying" includes a change in the aroma profile.

[0034] The booster effect is particularly desirable in fragrance compositions when applications are sought that feature a top note from which the odor is delivered particularly quickly and strongly, for example in air fresheners, in deodorants, or in chewing gum in the taste category.

[0035] The terms "compound" and "substance" are used interchangeably throughout this invention.

[0036] In the context of the present invention, the expression "C1-C4-alkyl" refers to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl. Preferably, the expression "C1-C4-alkyl" refers to C1-C3-alkyl (i.e. methyl, ethyl, n-propyl and isopropyl), and in particular to C1-C2-alkyl (i.e. methyl and ethyl).

[0037] R in compound (I) 1 , R 2 , R 3 and R 4 In one alternative definition of 2 , R 3 or R 4 One of them is R 1 Together with represents a double bond; R 2 , R 3 or R 4 The rest of the is hydrogen. This is, of course, 2 , R 3 or R 4 and R 1 and the bond between the carbon atom to which R is bonded.2 , R 3 or R 4 R 1 This means that a double bond is formed by combining with the bond formed with R. 2 R 1 Together with R represents a double bond. 3 and R 4 When R is hydrogen, this results in a compound of formula (I-1). 3 R 1 Together with R represents a double bond. 2 and R 4 When R is hydrogen, this results in a compound of formula (I-2). 4 R 1 Together with R represents a double bond. 2 and R 3 When is hydrogen, this results in a compound of formula (I-3).

[0038] [ka]

[0039] R 5 has the same meaning in all three compounds (I-1), (I-2) and (I-3), then these compounds are considered to be double bond isomers of each other.

[0040] The term "stereoisomer" as used in the context of the present invention specifically relates to optical isomers, such as enantiomers or diastereomers, the latter existing due to two or more stereocenters in the molecule. The compounds of formula (I) have at least one stereocenter, namely the carbon atom of the di- or tetrahydropyran ring adjacent to the oxygen ring atom bearing an isobutanol-2-yl- or isobutanol-2-yl-derived substituent. R 5 There may be additional stereocenters in the group, for example if it is sec-butyl or if it is -C(=O)-R 6 (where R 6is sec-butyl), the carbon atom marked with an asterisk in this sec-butyl group (-CH(CH3)CH2CH3) is the stereocenter in both cases. 1 , R 2 , R 3 and R 4 Yet another stereocenter present in compound (I) where is hydrogen is the carbon atom at position 4 of the tetrahydropyran ring which bears a methyl group.

[0041] In the context of the present invention, the term "pure enantiomer" is understood as a non-racemic mixture of a particular compound, in which the desired enantiomer is present in an enantiomeric excess of >90% ee.

[0042] In the context of the present invention, the term "pure diastereomer" is understood as a mixture of diastereomers of a particular compound, wherein the desired diastereomer is present in an amount of >90% relative to the total amount of diastereomers of said compound.

[0043] In the context of the present invention, the terms "Compound I", "Compound (I)" or "compound of formula (I)" refer to the form of the compound as obtained in the non-stereoselective process used for its preparation, unless it is defined as a specific stereoisomer or a mixture of specific stereoisomers. However, the term is also used when it is not necessary or possible to specify the stereochemistry of Compound (I) in more detail.

[0044] If in the following a compound of formula (I) is defined as being a specific defined compound (and not a mixture of different compounds I), this means that this compound comprises less than 5% by weight, preferably less than 3% by weight, in particular less than 1% by weight, of other compounds I relative to the total weight of the specific defined compound I and the other compound(s) I optionally present.

[0045] In mixtures containing different compounds (I), these may be 1 Base~R 4 Group definitions and / or R5 Preferably, the compounds in the mixture differ in the definition of the R 1 Base~R 4 They differ only in the definition of the groups, in particular R 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4 In the case where the remainder of R 5 has the same meaning) but R 5 Compound (I) in which R is not H 5 By the preparation process of compounds (I) where R is H or from other alcohol precursors which have to be converted into ether or ester precursors, such compounds can be easily obtained without any reaction if the reaction is not complete and / or if the isolation / purification step is not performed or is not performed to an adequate extent. 5 It may also include compounds (I) in which R 5 Compounds (I) in which is H are generally only present in small amounts, for example only at most 10% by weight, preferably at most 5% by weight and in particular at most 2% by weight, based on the total weight of all compounds (I) present in the mixture.

[0046] The notes set forth below regarding preferred definitions of the variables are valid on their own and preferably in combination with each other, where applicable, with respect to the compounds of formula (I) as defined herein and with respect to the compositions, uses and methods of the invention as defined herein.

[0047] Embodiment (Ex) of the present invention General and preferred embodiments Ex are summarized in the following, non-exclusive list: Further preferred embodiments will become apparent from the paragraphs following this list.

[0048] E.1 Formula (I):

[0049] [ka] (In the formula, R 1 , R 2 , R 3 and R 4 is hydrogen; or R 2 , R 3 or R 4 One of them is R 1 Together with represents a double bond; R 2 , R 3 or R 4 all of the remainder are hydrogen; R 5 is hydrogen, C1-C4-alkyl and -C(=O)-R 6 wherein R 6 is selected from the group consisting of hydrogen and C1-C4-alkyl or a mixture thereof [i.e. a mixture of compounds of different formula (I)], a stereoisomer thereof or a mixture of stereoisomers thereof; Alternatively, at least one compound of formula (I) and a compound of formula (II.1) and / or (II.2):

[0050] [ka] (In the formula, R 5 is as defined above) A mixture of one or both of the compounds.

[0051] E.2 R 2 , R 3 or R 4 One of them is R 1 Together with represents a double bond; R 2 , R 3 or R 4 The compound defined in embodiment E.1, wherein all of the remainder are hydrogen.

[0052] E.3 Compound (I-1):

[0053] [ka] That is, R 2 R 1 Together with R represents a double bond. 3 and R 4 The compound as defined in embodiment E.2, which is a compound of formula (I), wherein is hydrogen.

[0054] E.4 Compound (I-2):

[0055] [ka] That is, R 3 R 1 Together with R represents a double bond. 2 and R 4 The compound as defined in embodiment E.2, which is a compound of formula (I), wherein is hydrogen.

[0056] E.5 Compound (I-3):

[0057] [ka] That is, R 4 R 1 Together with R represents a double bond. 2 and R 3 The compound as defined in embodiment E.2, which is a compound of formula (I), wherein is hydrogen.

[0058] E.6 Compounds (I-1), (I-2) and (I-3):

[0059] [ka] wherein compound (I-1) is R 2 R 1 Together with R represents a double bond. 3 and R 4is hydrogen; compound (I-2) is a compound of formula (I) in which R 3 R 1 Together with R represents a double bond. 2 and R 4 is hydrogen; compound (I-3) is a compound of formula (I) in which R 4 R 1 Together with R represents a double bond. 2 and R 3 The compound as defined in embodiment E.2, which is a compound of formula (I), wherein is hydrogen.

[0060] E.7 The compound as defined in embodiment E.6, which is a mixture comprising compound (I-1), compound (I-3) and optionally also compound (I-2).

[0061] E.8 The compound as defined in embodiment E.6, which is a mixture comprising compound (I-2), compound (I-3) and optionally also compound (I-1).

[0062] E.9 The compound as defined in any of embodiments E.6 to E.8, which is a mixture comprising all three compounds (I-1), (I-2) and (I-3).

[0063] E.10. The compound as defined in any of embodiments E.6, E.7 or E.9, wherein compound (I-1) predominates and is present in an amount of at least 35% by weight, and wherein each of compounds (I-2) and (I-3) is present in an amount of less than 35% by weight, relative to the total weight of compounds (I-1), (I-2) and (I-3).

[0064] E.11 The compound defined in embodiment E.10, wherein compound (I-1) is present in an amount of at least 40% by weight and each of compounds (I-2) and (I-3) is present in an amount of less than 40% by weight, based on the total weight of compounds (I-1), (I-2) and (I-3).

[0065] E.12. The compound as defined in any of embodiments E.6, E.8 or E.9, wherein compound (I-2) predominates and is present in an amount of at least 40% by weight, and wherein each of compounds (I-1) and (I-3) is present in an amount of less than 40% by weight, relative to the total weight of compounds (I-1), (I-2) and (I-3).

[0066] E.13 The compound defined in embodiment E.12, wherein compound (I-2) is present in an amount of at least 45% by weight and each of compounds (I-1) and (I-3) is present in an amount of less than 45% by weight, based on the total weight of compounds (I-1), (I-2) and (I-3).

[0067] E.14 In all of the compounds (I-1), (I-2) and (I-3) present in the mixture, R 5 The compound as defined in any of embodiments E.6 to E.13, wherein

[0068] E.15 R 1 , R 2 , R 3 and R 4 A compound as defined in embodiment E.1, wherein is hydrogen.

[0069] E.16. The compound as defined in any of the embodiments E.1 to E.15, which is a mixture comprising at least one compound (I) and one or both of the compounds of formulae (II.1) and / or (II.2).

[0070] E.17 The compound as defined in embodiment E.16, which is a mixture comprising at least one of the compounds (I-1), (I-2) and / or (I-3) and further comprising one or both of the compounds of formulae (II.1) and / or (II.2).

[0071] E.18 The compound as defined in embodiment E.17, wherein the mixture comprises, as compound (I), compound (I-1), compound (I-3) and optionally also compound (I-2), and further comprises one or both of the compounds of formulae (II.1) and / or (II.2).

[0072] E.19 The compound as defined in any of embodiments E.16 to E.18, wherein in the mixture, compound(s) (I) predominates.

[0073] E.20 The compound defined in embodiment E.19, wherein in the mixture, the one or more compounds (I) are present in a total amount of at least 60% by weight, based on the total weight of all of the compounds (I), (II.1) and (II.2).

[0074] E.21 The compound defined in embodiment E.20, wherein the one or more compounds (I) are present in a total amount of at least 65% by weight, based on the total weight of all of compounds (I), (II.1) and (II.2).

[0075] E.22 If compound (I) is a mixture of different compounds (I) optionally also containing one or both of compounds (II.1) and / or (II.2) or a mixture of compound (I) with one or both of compounds (II.1) and / or (II.2), then R 5 A compound as defined in any of embodiments E.1 to E.21, wherein

[0076] E.23 R in all of the compounds (I), (II.1) and (II.2) present in the mixture 5 The compound as defined in any of embodiments E.16 to E.21, wherein

[0077] E.24 R 5 The compound as defined in any of embodiments E.1 to E.23, wherein is C1-C4-alkyl.

[0078] E.25 R 5 The compound defined in embodiment E.24, wherein is methyl or ethyl.

[0079] E.26 R 5 The compound defined in embodiment E.25, wherein is methyl.

[0080] E.27 R 5 The compound as defined in any of embodiments E.1 to E.23, wherein is hydrogen.

[0081] E.28 R 5 -C(=O)-R 6 where R 6 A compound as defined in any of embodiments E.1 to E.23, wherein is hydrogen or C1-C4-alkyl.

[0082] E.29 R 6 The compound defined in embodiment E.28, wherein is methyl or ethyl.

[0083] E.30 R 6 The compound defined in embodiment E.29, wherein is methyl.

[0084] E.31 A composition comprising a compound of formula (I) as defined in any of the embodiments E.1 to E.30, a mixture thereof [i.e. a mixture of compounds of different formula (I)], a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one further ingredient selected from the group consisting of fragrance chemicals different from compounds (I), (II.1) and (II.2), non-fragrance chemical carriers, antioxidants and deodorising actives.

[0085] E.32. The composition according to embodiment E.31, wherein at least one further component is selected from the group consisting of fragrance chemicals different from compounds (I), (II.1) and (II.2), surfactants, oil components, solvents, antioxidants and deodorising actives.

[0086] E.33 Geranyl acetate (3,7-dimethyl-2,6-octadien-1-yl acetate), α-hexylcinnamaldehyde, 2-phenoxyethyl isobutyrate (Phenirat 1), dihydromyrcerol (2,6-dimethyl-7-octen-2-ol), methyl dihydrojasmonate (preferably with a content of cis isomer of more than 60% by weight) (Hedione 9 , Hedione HC 9 ), 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopenta[g]benzopyran (Galaxolid 3 ), Tetrahydrolinalool (3,7-dimethyloctan-3-ol), Ethyl linalool, Benzyl salicylate, 2-Methyl-3-(4-tert-butylphenyl)propanal (Lysmeral 2 ), 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 (Herbaflorat 1 ), citronellol, citronellyl acetate, tetrahydrogeraniol, vanillin, linalyl acetate, styrolyl acetate (1-phenylethyl acetate), octahydro-2,3,8,8-tetramethyl-2-acetonaphthone and / or 2-acetyl-1,2,3,4,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene (Iso E Super 3 ), Hexyl Salicylate, 4-tert-Butylcyclohexyl Acetate (Oryclone 1 ), 2-tert-butylcyclohexyl acetate (Agrumex HC 1 ), α-ionone (4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one), n-α-methyl ionone, α-isomethyl ionone, coumarin, terpinyl acetate, 2-phenylethyl alcohol, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-carboxaldehyde (Lyral 3 ), α-amylcinnamaldehyde, ethylene brassylate, (E)- and / or (Z)-3-methylcyclopentadec-5-enone (Muscenon 9), 15-pentadec-11-enolide and / or 15-pentadec-12-enolide (Globalide 1 ), 15-Cyclopentadecanolide (Macrolide 1 ), 1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthalenyl)ethanone (Tonalid 10 ), 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol (Florol 9 ), 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol (Sandolen 1 ), cis-3-hexenyl acetate, trans-3-hexenyl acetate, trans-2 / cis-6-nonadienol, 2,4-dimethyl-3-cyclohexenecarboxaldehyde (Vertocitral 1 ), 2,4,4,7-tetramethyloct-6-en-3-one (Claritone 1 ), 2,6-Dimethyl-5-hepten-1-al (Melonal 2 ), borneol, 3-(3-isopropylphenyl)butanal (Florhydral 2 ), 2-methyl-3-(3,4-methylenedioxyphenyl)propanal (Helional 3 ), 3-(4-ethylphenyl)-2,2-dimethylpropanal (Florazon 1 ), 7-methyl-2H-1,5-benzodioxepin-3(4H)-one (Calone), 3,3,5-trimethylcyclohexyl acetate (preferably having a cis-isomer content of greater than 70% by weight), 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydronaphthalen-2-ol (Ambrinol S 1 ), 3-(4-tert-butylphenyl)-propanal (Bourgeonal 4 ), Ethyl 2-methylpentanoate (Manzanate 4 ), ethoxymethoxycyclododecane (Amberwood 1), 2,4-dimethyl-4,4a,5,9b-tetrahydroindeno[1,2-d][1,3]dioxin (Magnolan 1 ), (2-tert-butylcyclohexyl) acetate (Verdox 3 ) and 3-[5,5,6-trimethylbicyclo[2.2.1]hept-2-yl]cyclohexan-1-ol (Sandela 4 The composition according to any of embodiments E.31 or E.32, comprising at least one further fragrance chemical selected from the group consisting of:

[0087] E.34. The composition according to any of embodiments E.31 or E.32, comprising at least one further aroma chemical selected from the group consisting of methyl benzoate, benzyl acetate, geranyl acetate, 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol and linalool.

[0088] E.35 The composition according to any of embodiments E.31 or E.32, comprising at least one further aroma chemical selected from the group consisting of ethyl vanillin, vanillin, 2,5-dimethyl-4-hydroxy-2H-furan-3-one (furaneol) or 3-hydroxy-2-methyl-4H-pyran-4-one (maltol).

[0089] E.36 The composition according to any of embodiments E.31 to E.35, comprising at least one solvent 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.

[0090] E.37. A composition according to any of embodiments E.31-E.36, comprising at least one deodorant active selected from the group consisting of antiperspirants, esterase inhibitors, and antimicrobial agents.

[0091] E.38. A composition according to embodiment E.37, wherein the antiperspirant is selected from the group consisting of aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate, aluminum hydroxyalantoinate, aluminum tartrate chloride, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, and aluminum zirconium pentachlorohydrate.

[0092] E.39 The composition according to any of embodiments E.37 or E.38, wherein 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.

[0093] E.40 The antibacterial agent is selected from the group consisting of chitosan, phenoxyethanol, 5-chloro-2-(2,4-dichlorophenoxy)-phenol, 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)-urea, 2,4,4'-trichloro-2'-hydroxydiphenyl ether (triclosan), 4-chloro-3,5-dimethylphenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 3-methyl-4-(1-methylethyl)-phenol, 2-benzo[b]pyrrolidone ... The composition according to any of embodiments E.37 to E.39, wherein the compound is selected from the group consisting of diethyl-4-chlorophenol, 3-(4-chlorophenoxy)-propane-1,2-diol, 3-iodo-2-propynyl butylcarbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), phenoxyethanol, glycerol monocaprate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylic acid-N-alkylamides.

[0094] E.41 The composition according to any of embodiments E.31 to E.40, comprising at least one surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and zwitterionic surfactants.

[0095] E.42 The composition according to embodiment E.41, wherein at least one surfactant is an anionic surfactant.

[0096] E.43 The composition according to any of embodiments E.31 to E.42, comprising at least one antioxidant selected from the group consisting of pentaerythrityl, tetra-di-t-butyl hydroxyhydrocinnamate, nordihydroguaiaretic acid, ferulic acid, resveratrol, propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), ascorbyl palmitate, and tocopherol.

[0097] E.44 Guerbet alcohols based on fatty alcohols containing 6 to 18 carbon atoms, 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, Erucyl erucate, C 18 -C 38 Alkyl-hydroxycarboxylic acids and linear or branched C6-C 22 Esters with fatty alcohols, esters of linear and / or branched fatty acids with polyhydric alcohols, C6-C 22 Esters of fatty alcohols or Guerbet alcohols with aromatic carboxylic acids, esters of dicarboxylic acids with polyols containing 2-10 carbon atoms and 2-6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C 22 Fatty alcohol carbonates, Guerbet carbonates based on fatty alcohols containing 6 to 18 carbon atoms, benzoic acid and linear and / or branched C6-C 22The composition according to any of embodiments E.31 to E.43, comprising at least one oil component selected from the group consisting of esters with alcohols, linear or branched symmetric or asymmetric dialkyl ethers containing 6 to 22 carbon atoms per alkyl group, ring-opening products of epoxidized fatty acid esters with polyols, hydrocarbons, and mixtures thereof.

[0098] E.45 A composition according to any of embodiments E.31 to E.44 selected from the group consisting of perfume compositions, body care compositions, oral or dental hygiene products, hygiene articles, cleaning compositions, fabric detergent compositions, compositions for scent dispensers, food products, dietary supplements, pharmaceutical compositions and crop protection compositions.

[0099] E.46 Use of a compound of formula (I) as defined in any of the embodiments E.1 to E.30, a mixture thereof [i.e. a mixture of compounds of different formula (I)], a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of at least one compound of formula (I) with one or both compounds of formula (II.1) and / or (II.2) as aroma chemical.

[0100] E.47 Use as defined in embodiment 46 for imparting an olfactory impression.

[0101] E.48 Use as defined in embodiment 47 as a fragrance.

[0102] E.49 Use of a compound of formula (I) as defined in any one of embodiments E.1 to E.30, a mixture thereof [i.e. of a mixture of different compounds of formula (I)], a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of at least one compound of formula (I) with one or both of compounds of formula (II.1) and / or (II.2) for modifying and / or enhancing the odor of a composition.

[0103] E.50 Use as defined in embodiment 49 for modifying and / or enhancing the fragrance impression of a composition.

[0104] E.51 Use as defined in embodiment 50 for modifying and / or enhancing the fragrance impression of a fragranced composition.

[0105] E.52 Use as defined in embodiment 51 for modifying the fragrance impression / odor characteristics of a fragranced ready-to-use composition.

[0106] E.53 Use according to any of embodiments E.46 to E.52 in a composition selected from perfume compositions, body care compositions, oral or dental hygiene products, hygiene articles, cleaning compositions, fabric detergent compositions, compositions for scent dispensers, foods, dietary supplements, pharmaceutical compositions and crop protection compositions.

[0107] E.54 A method for preparing an aroma chemical composition comprising incorporating at least one compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of at least one compound of formula (I) with one or both of the compounds of formulae (II.1) and / or (II.2) as defined in any one of embodiments E.1 to E.30, into a target composition to provide an aroma chemical composition.

[0108] E.55. A method as defined in embodiment E.53 for preparing a fragranced composition.

[0109] E.56 A process as defined in embodiment E.54 for preparing a fragranced, ready-to-use composition, comprising incorporating into the ready-to-use composition at least one compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of at least one compound of formula (I) with one or both of the compounds of formulae (II.1) and / or (II.2), as defined in any one of embodiments E.1 to E.30.

[0110] E.57 A method for preparing a fragrance chemical composition comprising mixing at least one compound of formula (I), its stereoisomer, a mixture of stereoisomers thereof, as defined in any of embodiments E.1 to E.30, or a mixture of at least one compound of formula (I) with one or both of compounds of formulae (II.1) and / or (II.2), with at least one fragrance chemical different from compounds (I), (II.1) and (II.2), and / or with at least one non-fragrance chemical carrier, and / or with at least one antioxidant, and / or with at least one deodorising active.

[0111] E.58 The method defined in embodiment E.56, wherein the at least one fragrance chemical different from compounds (I), (II.1) and (II.2), the at least one non-fragrance chemical carrier, the at least one antioxidant, and the at least one deodorizing active are as defined in embodiments E.31 to E.44.

[0112] E.59 A method for modifying and / or enhancing the fragrance of a composition comprising incorporating into said composition at least one compound of formula (I), its stereoisomer, or a mixture of its stereoisomers, optionally mixed with one or both of the compounds of formula (II.1) and / or (II.2).

[0113] E.60 The method of embodiment E.58 for modifying and / or enhancing the fragrance impression of a fragrance composition.

[0114] E.61 The method of embodiment E.59 for modifying and / or enhancing the fragrance impression of a fragranced composition.

[0115] E.62 The method of embodiment E.60, comprising incorporating at least one compound of formula (I), its stereoisomer, or a mixture of its stereoisomers, optionally mixed with one or both of the compounds of formulae (II.1) and / or (II.2), into a ready-to-use composition to modify and / or enhance the fragrance impression of the fragranced ready-to-use composition.

[0116] E.63 The method defined in any of embodiments E.54 to E.62, wherein the composition is selected from the group consisting of a perfume composition, a body care composition, an oral or dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food product, a dietary supplement, a pharmaceutical composition, and a crop protection composition.

[0117] E.64 A process for preparing a compound of formula (I) as defined in any of the embodiments E.1 to E.30, a mixture thereof [i.e. a mixture of compounds of different formulae (I)], a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of at least one compound of formula (I) with one or both compounds of formulae (II.1) and / or (II.2), comprising the following steps: (a) 3-Methylbut-3-en-1-ol (isoprenol) is reacted with 3-hydroxy-2,2-dimethyl-propanal (hydroxypivalinaldehyde) in an acidic medium to give the compound of formula (I') and, optionally, the compounds of formula (II'.1) and / or (II'.2)

[0118] [ka] (In the formula, R 2 , R 3 or R 4 One of them is R 1 Together with represents a double bond; R 2 , R 3 or R 4 the rest are all hydrogen) obtaining a reaction mixture containing one or both of the compounds of (b) optionally isolating the compound of formula (I') and, if present, compounds (II'-1) and (II'-2) from the reaction mixture obtained in step (a) or enriching it in the reaction mixture obtained in step (a); (c) a compound of formula (I) or a compound of formula (I') 1 , R 2 , R 3 and R 4is hydrogen), the reaction mixture obtained in step (a) or the product obtained in step (b) is subjected to a hydrogenation reaction to prepare a compound of formula (I'), 1 , R 2 , R 3 and R 4 is hydrogen; (d) R 5 is not hydrogen is prepared: subjecting the reaction mixture obtained in step (a) or the product obtained in step (b) or the product obtained in step (c) to an etherification reaction or an esterification reaction; (e) a compound of formula (I), 1 , R 2 , R 3 and R 4 is hydrogen, and R 5 is not hydrogen) is prepared, and if step (c) has not been carried out: subjecting the product obtained in step (d) to a hydrogenation reaction; and (f) optionally subjecting the product obtained in step (b), or step (c), or step (d), or step (e) to a purification step. The above method.

[0119] E.65 Compounds of formula (I) as defined in any of embodiments E.1 to E.30, wherein R 5 is C1-C4-alkyl and -C(=O)-R 6 a mixture thereof [i.e. a mixture of different compounds of formula (I)], a stereoisomer thereof, or a mixture of stereoisomers thereof, comprising the steps of: (i) 3-hydroxy-2,2-dimethyl-propanal (hydroxypivalinaldehyde) is subjected to an etherification reaction or an esterification reaction to obtain a compound represented by formula 3:

[0120] [ka] (In the formula, R 5a is C1-C4-alkyl and -C(=O)-R6 (selected from the group consisting of obtaining a reaction mixture comprising the compound of formula (I); (ii) optionally isolating the compound of formula 3 from the reaction mixture obtained in step (i) or enriching it in the reaction mixture obtained in step (i); (iii) reacting the reaction mixture obtained in step (i) or the product obtained in step (ii) with 3-methylbut-3-en-1-ol (isoprenol) in the presence of a BF source to obtain a compound of formula (I), 5 is C1-C4-alkyl and -C(=O)-R 6 obtaining a reaction mixture comprising: (iv) a compound of formula (I) 1 , R 2 , R 3 and R 4 is hydrogen, and R 5 is C1-C4-alkyl and -C(=O)-R 6 (selected from the group consisting of): subjecting the product obtained in step (iii) to a hydrogenation reaction; (v) optionally subjecting the product obtained in step (iii) or step (iv) to a purification step. The above method.

[0121] E.66 A product obtainable by the process of any of embodiments E.63 to E.65.

[0122] Compound (I) In one embodiment, in compound (I), R 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4 In another embodiment, in compound (I), R 1 , R 2 , R 3 and R 4is hydrogen.

[0123] However, preferably, in compound (I), R 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4 The remainder is all hydrogen.

[0124] In a more preferred embodiment, compound (I) is compound (I-1).

[0125] In another more preferred embodiment, compound (I) is compound (I-2).

[0126] In yet another more preferred embodiment, compound (I) is compound (I-3).

[0127] Among the compounds (I-1), (I-2) and (I-3), the compounds (I-1) and (I-2) are more preferred, and the compound (I-1) is particularly preferred.

[0128] In another more preferred embodiment, compound (I) is a mixture of two or more, in particular two or three, different compounds (I).

[0129] R 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4Compound (I), in which all the rest are hydrogen, is accessible by a synthesis method that can give rise to a mixture containing at least two of compounds (I-1), (I-2) and (I-3). It is possible to separate this mixture into single compounds. However, as can be seen, said mixture also has very advantageous olfactory properties. For this reason, it is not necessary to separate said mixture into different compounds (I). Thus, in a particular embodiment, the present invention relates to a mixture containing at least two of compounds (I-1), (I-2) and (I-3). In a more specific embodiment, the present invention relates to a mixture containing compound (I-1), compound (I-3) and optionally also compound (I-2). In particular, the present invention relates to a mixture containing all three compounds (I-1), (I-2) and (I-3). In such a mixture containing at least two of compounds (I-1), (I-2) and (I-3) formed in the manufacturing process, it will be understood that R is not present in all compounds (I) present in the mixture. 5 have the same meaning; that is, compounds (I-1), (I-2) and (I-3) are double bond isomers of each other.

[0130] In a mixture containing all three compounds (I-1), (I-2) and (I-3), generally, either compound (I-1) or compound (I-2) predominates; that is, it is present in a higher amount than either of the other two compounds (but not necessarily higher than the sum of the other two compounds). In a particular embodiment, compound (I-1) predominates and is present in an amount of at least 35% by weight (wherein it is to be understood that each of compounds (I-2) and (I-3) is present in an amount less than 35% by weight), preferably at least 40% by weight (wherein it is to be understood that each of compounds (I-2) and (I-3) is present in an amount less than 40% by weight), based on the total weight of compounds (I-1), (I-2) and (I-3). In another particular embodiment, compound (I-2) is predominant and is present in an amount of at least 40% by weight (wherein it is to be understood that each of compounds (I-1) and (I-3) is present in an amount less than 40% by weight), preferably at least 45% by weight (wherein it is to be understood that each of compounds (I-1) and (I-3) is present in an amount less than 45% by weight), based on the total weight of compounds (I-1), (I-2) and (I-3). The mixture in which compound (I-1) is predominant generally has a stronger odor than the mixture in which compound (I-2) is predominant. However, the latter mixture is also interesting, since in some applications a less intense odor profile may be advantageous.

[0131] Compound (I) is accessible, inter alia, by the Prins reaction of isoprenol with hydroxypivalinaldehyde (see the process description below for details). Depending on the reaction conditions, the formation of the desired dihydro- or tetrahydropyran ring can be mediated by the formation of the corresponding cyclic acetal(s) (the isobutyl-derived group (-C(CH)-CH-OR) at the 2-position). 5) competes with the formation of 1,3-dioxane) with ... 5 is R in one or more compounds (I) present in the mixture. 5 The product of the Prins reaction may be subjected to further etherification or esterification reactions, so that due to incomplete reaction the resulting mixture may contain some alcohol, where R 5 remains hydrogen.

[0132] It is possible to separate the compound(s) (I) from the acetals (II.1) and (II.2). However, as can be seen, these mixtures also have very advantageous olfactory properties. Therefore, such a separation is not necessary. In this mixture, the compound(s) (I) predominate. This means that in a mixture that contains one or more compounds (I) as well as one or both of the acetals (II.1) and (II.2), the one or more compounds (I) are present in a total amount of more than 50% by weight, based on the total weight of all the compounds (I), (II.1) and (II.2). Preferably, the one or more compounds (I) are present in a total amount of at least 60% by weight, in particular at least 65% by weight, based on the total weight of all the compounds (I), (II.1) and (II.2).

[0133] In a preferred embodiment, in compound (I), R 5 is C1-C4-alkyl. More preferably, R 5 is methyl or ethyl, in particular methyl.

[0134] In another preferred embodiment, in compound (I), R 5 is hydrogen.

[0135] In yet another preferred embodiment, in compound (I), R 5 is -C(=O)-R 6 where R 6 is hydrogen or C1-C4-alkyl. More preferably, R 6 is methyl or ethyl, in particular methyl.

[0136] In one particular embodiment (embodiment 1.1), compound (I) is compound (I-1), R 5 is H.

[0137] In another particular embodiment (embodiment 1.2), compound (I) is compound (I-2), R 5 is H.

[0138] In another particular embodiment (embodiment 1.3), compound (I) is compound (I-3), R 5 is H.

[0139] In another particular embodiment (embodiment 1.4), compound (I) is a mixture of at least two of compounds (I-1), (I-2) and (I-3), in which in each case R 5 is H.

[0140] In another particular embodiment (embodiment 1.5), compound (I) is a mixture of compound (I-1) with one or both of compounds (I-2) and (I-3), in which in each case R 5 is H.

[0141] In another particular embodiment (embodiment 1.6), compound (I) is a mixture of compound (I-2) with one or both of compounds (I-1) and (I-3), in which in each case R 5 is H.

[0142] In another particular embodiment (embodiment 1.7), compound (I) is a mixture of compound (I-3) with one or both of compounds (I-1) and (I-2), in which in each case R 5 is H.

[0143] In another particular embodiment (embodiment 1.8), compound (I) is a mixture of one or both of compounds (I-1), (I-2) and (I-3), and one or both of compounds (II.1) and (II.2), in each case R 5 is H.

[0144] In another particular embodiment (embodiment 1.9), compound (I) is a mixture of compound (I-2), one or both of compounds (I-1) and (I-3), and one or both of compounds (II.1) and (II.2), in each case R 5 is H.

[0145] In another particular embodiment (embodiment 1.10), compound (I) is a mixture of compound (I-3), one or both of compounds (I-1) and (I-2), and one or both of compounds (II.1) and (II.2), in each case R 5 is H.

[0146] In another particular embodiment (embodiment 1.11), compound (I) is R 1 , R 2 , R 3 and R 4 is hydrogen and R 5 is H.

[0147] In another particular embodiment (embodiment 1.12), compound (I) is R 1 , R 2 , R 3 and R 4 is a mixture of compounds (I), in which R is hydrogen, and one or both of compounds (II.1) and (II.2), in which in each case R 5 is H.

[0148] In another particular embodiment (embodiment 2.1), compound (I) is compound (I-1), R 5 is methyl.

[0149] In another particular embodiment (embodiment 2.2), compound (I) is compound (I-2), R 5 is methyl.

[0150] In another particular embodiment (embodiment 2.3), compound (I) is compound (I-3), R 5 is methyl.

[0151] In another particular embodiment (embodiment 2.4), compound (I) is a mixture of at least two of compounds (I-1), (I-2) and (I-3), in which in each case R 5 is methyl.

[0152] In another particular embodiment (embodiment 2.5), compound (I) is a mixture of compound (I-1) with one or both of compounds (I-2) and (I-3), in which in each case R 5 is methyl.

[0153] In another particular embodiment (embodiment 2.6), compound (I) is a mixture of compound (I-2) with one or both of compounds (I-1) and (I-3), in which in each case R 5 is methyl.

[0154] In another particular embodiment (embodiment 2.7), compound (I) is a mixture of compound (I-3) with one or both of compounds (I-1) and (I-2), in which in each case R 5 is methyl.

[0155] In another particular embodiment (embodiment 2.8), compound (I) is a mixture of one or both of compounds (I-1), (I-2) and (I-3), and one or both of compounds (II.1) and (II.2), in each case R 5 is methyl.

[0156] In another particular embodiment (embodiment 2.9), compound (I) is a mixture of compound (I-2), one or both of compounds (I-1) and (I-3), and one or both of compounds (II.1) and (II.2), in each case R 5 is methyl.

[0157] In another particular embodiment (embodiment 2.10), compound (I) is a mixture of compound (I-3), one or both of compounds (I-1) and (I-2), and one or both of compounds (II.1) and (II.2), in each case R 5 is methyl.

[0158] In another particular embodiment (embodiment 2.11), compound (I) is R 1 , R 2 , R 3 and R 4 is hydrogen and R 5 is compound (I), in which

[0159] In another particular embodiment (embodiment 2.12), compound (I) is R 1 , R 2 , R 3 and R 4 is a mixture of compounds (I) in which R is hydrogen and one or both of compounds (II.1) and (II.2), in which in each case R 5 is methyl.

[0160] In another particular embodiment (embodiment 3.1), compound (I) is compound (I-1), R 5 is ethyl.

[0161] In another particular embodiment (embodiment 3.2), compound (I) is compound (I-2), R 5 is ethyl.

[0162] In another specific embodiment (embodiment 3.3), compound (I) is compound (I-3), R 5 is ethyl.

[0163] In another particular embodiment (embodiment 3.4), compound (I) is a mixture of at least two of compounds (I-1), (I-2) and (I-3), in which in each case R 5 is ethyl.

[0164] In another particular embodiment (embodiment 3.5), compound (I) is a mixture of compound (I-1) with one or both of compounds (I-2) and (I-3), in which in each case R 5 is ethyl.

[0165] In another particular embodiment (embodiment 3.6), compound (I) is a mixture of compound (I-2) with one or both of compounds (I-1) and (I-3), in which in each case R 5 is ethyl.

[0166] In another particular embodiment (embodiment 3.7), compound (I) is a mixture of compound (I-3) with one or both of compounds (I-1) and (I-2), in which in each case R 5 is ethyl.

[0167] In another particular embodiment (embodiment 3.8), compound (I) is a mixture of one or both of compounds (I-1), (I-2) and (I-3), and one or both of compounds (II.1) and (II.2), in each case R 5 is ethyl.

[0168] In another particular embodiment (embodiment 3.9), compound (I) is a mixture of compound (I-2), one or both of compounds (I-1) and (I-3), and one or both of compounds (II.1) and (II.2), in each case R 5 is ethyl.

[0169] In another specific embodiment (embodiment 3.10), compound (I) is a mixture of compound (I-3), one or both of compounds (I-1) and (I-2), and one or both of compounds (II.1) and (II.2), in each case R 5 is ethyl.

[0170] In another particular embodiment (embodiment 3.11), compound (I) is R 1 , R 2 , R 3 and R 4 is hydrogen and R 5 is compound (I), in which

[0171] In another particular embodiment (embodiment 3.12), compound (I) is R 1 , R 2 , R 3 and R 4 is a mixture of compounds (I), in which R is hydrogen, and one or both of compounds (II.1) and (II.2), in which in each case R 5 is ethyl.

[0172] In another particular embodiment (embodiment 4.1), compound (I) is compound (I-1), R 5 is -C(=O)-CH3.

[0173] In another particular embodiment (embodiment 4.2), compound (I) is compound (I-2), R 5 is -C(=O)-CH3.

[0174] In another specific embodiment (embodiment 4.3), compound (I) is compound (I-3), R 5is -C(=O)-CH3.

[0175] In another particular embodiment (embodiment 4.4), compound (I) is a mixture of at least two of compounds (I-1), (I-2) and (I-3), in which in each case R 5 is -C(=O)-CH3.

[0176] In another particular embodiment (embodiment 4.5), compound (I) is a mixture of compound (I-1) with one or both of compounds (I-2) and (I-3), in which in each case R 5 is -C(=O)-CH3.

[0177] In another particular embodiment (embodiment 4.6), compound (I) is a mixture of compound (I-2) with one or both of compounds (I-1) and (I-3), in which in each case R 5 is -C(=O)-CH3.

[0178] In another particular embodiment (embodiment 4.7), compound (I) is a mixture of compound (I-3) with one or both of compounds (I-1) and (I-2), in which in each case R 5 is -C(=O)-CH3.

[0179] In another particular embodiment (embodiment 4.8), compound (I) is a mixture of one or both of compounds (I-1), (I-2) and (I-3), and one or both of compounds (II.1) and (II.2), in each case R 5 is -C(=O)-CH3.

[0180] In another particular embodiment (embodiment 4.9), compound (I) is a mixture of compound (I-2), one or both of compounds (I-1) and (I-3), and one or both of compounds (II.1) and (II.2), in each case R 5 is -C(=O)-CH3.

[0181] In another specific embodiment (embodiment 4.10), compound (I) is a mixture of compound (I-3), one or both of compounds (I-1) and (I-2), and one or both of compounds (II.1) and (II.2), in each case R 5 is -C(=O)-CH3.

[0182] In another particular embodiment (embodiment 4.11), compound (I) is R 1 , R 2 , R 3 and R 4 is hydrogen and R 5 is compound (I), where is -C(=O)-CH3.

[0183] In another particular embodiment (embodiment 4.12), compound (I) is R 1 , R 2 , R 3 and R 4 is a mixture of compounds (I), in which R is hydrogen, and one or both of compounds (II.1) and (II.2), in which in each case R 5 is -C(=O)-CH3.

[0184] In another specific embodiment (embodiment 5.1), compound (I) is compound (I-1), R 5 is -C(=O)-CH2CH3.

[0185] In another specific embodiment (embodiment 5.2), compound (I) is compound (I-2), R 5 is -C(=O)-CH2CH3.

[0186] In another specific embodiment (embodiment 5.3), compound (I) is compound (I-3), R 5 is -C(=O)-CH2CH3.

[0187] In another particular embodiment (embodiment 5.4), compound (I) is a mixture of at least two of compounds (I-1), (I-2) and (I-3), in which in each case R 5 is -C(=O)-CH2CH3.

[0188] In another particular embodiment (embodiment 5.5), compound (I) is a mixture of compound (I-1) with one or both of compounds (I-2) and (I-3), in which in each case R 5 is -C(=O)-CH2CH3.

[0189] In another particular embodiment (embodiment 5.6), compound (I) is a mixture of compound (I-2) with one or both of compounds (I-1) and (I-3), in which in each case R 5 is -C(=O)-CH2CH3.

[0190] In another particular embodiment (embodiment 5.7), compound (I) is a mixture of compound (I-3) with one or both of compounds (I-1) and (I-2), in which in each case R 5 is -C(=O)-CH2CH3.

[0191] In another particular embodiment (embodiment 5.8), compound (I) is a mixture of one or both of compounds (I-1), (I-2) and (I-3), and one or both of compounds (II.1) and (II.2), in each case R 5 is -C(=O)-CH2CH3.

[0192] In another particular embodiment (embodiment 5.9), compound (I) is a mixture of compound (I-2), one or both of compounds (I-1) and (I-3), and one or both of compounds (II.1) and (II.2), in each case R 5 is -C(=O)-CH2CH3.

[0193] In another specific embodiment (embodiment 5.10), compound (I) is a mixture of compound (I-3), one or both of compounds (I-1) and (I-2), and one or both of compounds (II.1) and (II.2), in each case R 5 is -C(=O)-CH2CH3.

[0194] In another particular embodiment (embodiment 5.11), compound (I) is R 1 , R 2 , R 3 and R 4 is hydrogen and R 5 is compound (I), where is -C(=O)-CH2CH3.

[0195] In another specific embodiment (embodiment 5.12), compound (I) is R 1 , R 2 , R 3 and R 4 is a mixture of compounds (I), in which R is hydrogen, and one or both of compounds (II.1) and (II.2), in which in each case R 5 is -C(=O)-CH2CH3.

[0196] Among the above embodiments, embodiments x.1 to x.6, x.8 and x.9 are particularly preferred. More preferred are embodiments x.4 to x.6 and x.8, particularly embodiments x.5, x.6 and x.8 (where x. represents the numbers 1. to 5. in the above embodiments 1.1 to 5.12).

[0197] Synthesis of Compound (I) Compounds of formula (I) can be prepared by the methods described below or in the synthetic illustrations of the Examples, or by standard methods of organic chemistry. The substituents, variables and subscripts are as defined above for formula (I) unless otherwise specified.

[0198] More precisely, compound (I) can be prepared by standard methods for preparing cyclic ethers, for example by the Prins reaction, which involves reacting isoprenol (3-methylbut-3-en-1-ol) (1) with 3-hydroxy-2,2-dimethyl-propanal (hydroxypivalaldehyde) (2), as shown in Scheme 1 (Method A) below. The reaction of (1) with (2) is generally carried out under acidic conditions. This reaction is carried out by cleaving an alcohol compound (I) (wherein R 5 is H [hereinafter named compound (I')], R 2 , R 3 or R 4 One of them is R 1 Together with represents a double bond; R 2 , R 3 or R 4 The remainder of R is hydrogen. 5 The alcohol is etherified or esterified to give compound (I), where R is different from H. 1 , R 2 , R 3 and R 4 is hydrogen), compound (I') (wherein R 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4 and if desired, the hydrogenated product is etherified or esterified to obtain a compound of formula (wherein R 5 is different from H), or to obtain compound (I') (wherein R 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4 The etherification product or esterification product (wherein all of the remainder is hydrogen) is subjected to a hydrogenation reaction.

[0199] Scheme 1:

[0200] [ka]

[0201] In the reaction product (I') of Scheme 1, R 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4 The remainder is all hydrogen.

[0202] As already explained, depending on the reaction conditions, compound(s) I' can be obtained in admixture with one or both of the acetals (II.1) and (II.2).

[0203] Thus, one aspect of the present invention relates to a process for preparing a compound of formula (I) as defined above, a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I) or a mixture of at least one compound of formula (I) with one or both of the compounds of formulae (II.1) and / or (II.2), comprising the following steps: (a) 3-Methylbut-3-en-1-ol (isoprenol) ((1) in Scheme 1 above) and 3-hydroxy-2,2-dimethyl-propanal (hydroxypivalinaldehyde) ((2) in Scheme 1 above) are reacted in an acidic medium to produce one or more different compounds of formula (I'), optionally mixed with one or both of compounds (II'-1) and (II'-2):

[0204] [ka] (In the formula, R 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4the rest are all hydrogen)

[0205] [ka] obtaining a reaction mixture comprising: (b) optionally isolating one or more compounds of formula (I') or a mixture of at least one compound of formula (I') with one or both of the compounds of formula (II'.1) and / or (II'.2) [if the latter is formed in step (a)] from the reaction mixture obtained in step (a) or enriching it / them in the reaction mixture obtained in step (a); (c) a compound of formula (I) or a compound of formula (I') 1 , R 2 , R 3 and R 4 is hydrogen), the reaction mixture obtained in step (a) or the product obtained in step (b) is subjected to a hydrogenation reaction to prepare a compound of formula (I'), 1 , R 2 , R 3 and R 4 is hydrogen; (d) R 5 is not hydrogen is prepared: subjecting the reaction mixture obtained in step (a) or the product obtained in step (b) or the product obtained in step (c) to an etherification reaction or an esterification reaction; (e) a compound of formula (I), 1 , R 2 , R 3 and R 4 is hydrogen, and R 5 is not hydrogen) is prepared, and if step (c) has not been carried out: subjecting the product obtained in step (d) to a hydrogenation reaction; and (d) optionally subjecting the product obtained in step (b), or step (c), or step (d), or step (e) to a purification step. The present invention relates to the above method, comprising:

[0206] In step (a) (reflected in Scheme 1), isoprenol (1) and hydroxypivalinaldehyde (HPA) (2) undergo an addition reaction in an acidic medium to give R 5 is H and R 2 , R 3 or R 4 One of them is R 1 Together with represents a double bond, while R 2 , R 3 or R 4 wherein all of the remainder are hydrogen. This reaction can be considered to belong to the family of reactions known in the art as Prins reactions.

[0207] (1) and (2) are usually utilized in a molar ratio of 0.9:1 to 1.5:1, preferably 1:1 to 1.3:1. It is advantageous to use a slight excess of (1) to avoid the formation of acetals as by-products, which can predominate when (2) is used in excess.

[0208] The acidic medium in step (a) is provided by carrying out the reaction in the presence of an acid, preferably a Bronsted acid.

[0209] The Bronsted acid used in the reaction may be any Bronsted acid known in the art, and is preferably selected from strong Bronsted acids such as hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid (more precisely 10-camphorsulfonic acid), or strong acid cation exchange resins.

[0210] The term "strong acid cation exchanger" refers to a cation exchanger that has a strongly acidic group. +This refers to cation exchangers of the type. The strongly acidic groups are generally sulfonic acid groups; these are generally attached to a polymer matrix, which may be, for example, gel-like and / or macroporous. Styrene (co)polymers containing sulfonic acid groups are preferred, especially styrene-divinylbenzene copolymers containing sulfonic acid groups. Commercial examples of such cation exchangers are Lewatit® (Lanxess), Purolite® (The Purolite Company), Dowex® (Dow Chemical Company), Amberlite® (Rohm and Haas Company), Amberlyst® (Rohm and Haas Company). Preferred strongly acidic cation exchangers are: Lewatit® K 1221, Lewatit® K 1461, Lewatit® K 2431, Lewatit® K 2620, Lewatit® K 2621, Lewatit® K 2629, Lewatit® K 2649, Amberlite® FPC 22, Amberlite® FPC 23, Amberlite® IR. 120, Amberlyst® 131, Amberlyst® 15, Amberlyst® 31, Amberlyst® 35, Amberlyst® 36, Amberlyst® 39, Amberlyst® 46, Amberlyst® 70, Purolite® SGC650, Purolite® C100H, Purolite® C150H, Dowex® 50X8, Serdolit® red, and Nation® NR-50. In particular, resins of the Amberlyst® brand from Rohm and Haas are used, very particularly Amberlyst® 131 resin. Alternatively, the abovementioned cation exchangers can be perfluorinated ion exchange resins, for example those sold under the Nafion® brand from DuPont.

[0211] The Bronsted acid, which is different from the acidic cation exchange resin, is generally used in catalytic amounts. For example, the Bronsted acid can be used in an amount of 0.01 to 20 mol%, preferably 0.05 to 15 mol%, in particular 0.1 to 10 mol%, based on 1 mol of starting compound (1) and (2) used in smaller amounts. When (1) and (2) are used in equimolar amounts, the above percentages are of course based on 1 mol of either starting compound.

[0212] The amount of strongly acidic cation exchanger is not very important, but is generally used in catalytic amounts, taking into account economic and process aspects. Usually, the strongly acidic cation exchanger is used in an amount of about 5 to about 40% by weight, preferably about 10 to about 40% by weight, particularly preferably about 15 to about 30% by weight, based in each case on the total weight of (1) and (2). Here, the above figures refer to ready-to-use cation exchangers, which are generally pretreated with water and therefore may contain water in an amount of up to about 70% by weight, preferably about 30 to about 70% by weight, particularly preferably about 40 to about 70% by weight. Thus, especially in the case of discontinuous procedures, the addition of further water when carrying out the above steps may not be necessary. The particular strongly acidic cation exchangers can be used individually or in the form of mixtures.

[0213] Preferably, the Bronsted acid is selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid and 10-camphorsulfonic acid. In a particular embodiment, methanesulfonic acid or toluenesulfonic acid is used as the acid.

[0214] If an acid different from the acidic cation exchanger is used in the reaction in step (a), the reaction is generally carried out in a suitable organic solvent that is inert under the reaction conditions of step (a). Suitable solvents are, for example, alkanes (e.g. pentane or hexane), halogenated C1-C4-alkanes (e.g. dichloromethane, chloroform or dichloroethane), cycloalkanes (e.g. cyclohexane), aromatic hydrocarbons (e.g. toluene and xylene), aliphatic ethers (e.g. diethyl ether, diisopropyl ether or methyl-tert-butyl ether), cyclic ethers (e.g. tetrahydrofuran or dioxane) or carboxylic acid esters (e.g. ethyl acetate). The particular solvents can be used alone or in the form of a mixture with one another. In particular, aromatic hydrocarbons, very particularly toluene, are used. If an acidic cation exchanger is used, the reaction can also be carried out in the presence of a solvent that is inert under the reaction conditions. Suitable solvents are those listed above. Generally, however, when a strongly acidic cation exchanger is used as the Bronsted acid, the reaction is carried out neat (i.e. without the addition of an organic solvent).

[0215] The reactants can in principle be contacted with each other in any desired order. For example, isoprenol and hydroxypivalinaldehyde, optionally dissolved or dispersed in an inert solvent, can be placed first and mixed together. The Brönsted acid can then be added to the resulting mixture. This acid can be added in one go or can be added gradually, either continuously or in several portions. Alternatively, isoprenol and Brönsted acid, optionally dissolved or dispersed in an inert solvent, can be placed first and hydroxypivalinaldehyde can then be added. Alternatively, hydroxypivalinaldehyde can be mixed with Brönsted acid first and then this mixture can be mixed with isoprenol. As a further alternative, all reactants can be added simultaneously to the reaction vessel.

[0216] In a particular embodiment, isoprenol and hydroxypivalinaldehyde are mixed and dissolved or dispersed in an inert solvent, and the Bronsted acid is added in one portion or, preferably, added gradually, either continuously or in several portions.

[0217] Suitably, the water formed in the reaction is removed, typically by distillation, to facilitate the reaction.

[0218] The reaction temperature in step (a) depends on various factors, in particular on the acidity and the amount of Bronsted acid used, and can be determined in each individual case by the person skilled in the art, for example by simple preliminary tests. In general, the conversion in step (a) is carried out at a temperature in the range of 20-150° C., preferably in the range of 50-130° C., more preferably in the range of 100-120° C. In order to remove water, it is expedient to carry out the reaction at the reflux point of the reaction mixture, which in turn depends, inter alia, on the selected solvent.

[0219] Step (a) can be followed by an optional isolation step (b), for example by treating the reaction mixture obtained with an aqueous base, such as aqueous sodium bicarbonate. The organic phase containing compound (I') can then be used in step (c) or (d), either directly or after partial or complete removal of the solvent. However, preferably, the organic phase is concentrated and the crude product thus obtained is then used directly in step (c) or (d) or is preferably subjected to a further purification step, such as distillation or chromatography, in particular distillation.

[0220] When the reaction in step (a) is carried out neat in the presence of a cation exchange resin as a Bronsted acid, the work-up is generally carried out by first adding a solvent (e.g., a polar organic solvent that is insoluble or only slightly soluble in water and suitable for dissolving the obtained reaction product, such as ethyl acetate or dichloromethane) to the reaction. It is then convenient to filter the diluted mixture to remove the cation exchange resin used as a Bronsted acid. The above-mentioned work-up can then be carried out.

[0221] Step (a) generally produces a mixture containing at least two of the three double bond isomers (I-1), (I-2) and (I-3), most frequently all three (I-1), (I-2) and (I-3). This mixture can be used as is in step (c) or (d). Alternatively, a separation step can be included in step (b). The simple distillation step mentioned above as an optional purification step in the work-up step (b) is generally not suitable for separating the three double bond isomers. However, they can also be obtained in pure or at least enriched form in a rectification (fractional distillation) step. The purity depends on the number of theoretical plates in the fractional distillation column. Alternatively, high performance chromatography such as HPLC can be used.

[0222] Steps (a) and (b), if performed, 5 is hydrogen to produce compound (I).

[0223] Under certain reaction conditions, step (a) may also produce one or both of the acetal compounds (II.1) and (II.2). These may be primarily removed in step (b), but as mentioned above, separation is not necessary since they have no negative effect on the odor profile. Thus, R 5The following remarks for the further transformation of compound (I) where is hydrogen [steps (c), (d), (e) and (f)] also relate to the further transformation of compound (I) mixed with compounds (II.1) and / or (II.2).

[0224] R 1 , R 2 , R 3 and R 4 When a compound (I) is obtained in which is hydrogen, either a hydrogenation step (c) or a hydrogenation step (e) is carried out.

[0225] In principle, the hydrogenation can be achieved by using any hydrogenation method known in the art to be suitable for similar transformations. Preferably, the hydrogenation is carried out by using gaseous hydrogen as a reducing agent in the presence of a catalyst that typically contains at least one transition metal, in particular a transition metal belonging to group IVB, VIIIB or IB of the periodic table (CAS version), such as zirconium, palladium, platinum, iron, cobalt, nickel, rhodium, iridium, ruthenium or copper. These metals can be present in the catalyst in the form of one of their salts, oxides or complexes, or in metallic form. A preferred metal in this regard is nickel, especially in the form of Raney nickel. The hydrogenation in step (c) or (e) can be carried out analogously to the transformations described, for example, in JH Tyman et al., Tetrahedron Lett. 1970, 11, 4507; VH Rawal et al., J. Org. Chem. 1993, 58, 7718; BM Trost et al., J. Am. Chem. Soc. 2006, 128, 6745; L. Coulombel et al., Eur. J. Org. Chem. 2009, 33, 5788; and PL Alsters et al., Org. Process Res. Dev. 2010, 14, 259.

[0226] The hydrogenation in step (c) or (e) can be carried out without a solvent, but is preferably carried out in the presence of a solvent which is inert under the hydrogenation conditions, such as in particular a protic organic solvent, preferably selected from C1-C6-alkanols, in particular a protic organic solvent selected from methanol, ethanol and isopropanol.

[0227] The hydrogenation is typically carried out at a hydrogen pressure in the range of 1 to 2 bar, preferably in the range of 1 to 1.5 bar, in particular in the range of 1 to 1.2 bar. The temperature is usually in the range of 10 to 50°C, preferably in the range of 20 to 40°C (e.g., 20 to 30°C or 20 to 25°C).

[0228] Work-up of the reaction mixture obtained in step (c) or (e) and isolation of the hydrogenated compound can be achieved in a conventional manner, for example by filtration and removal of the solvent (e.g. under reduced pressure). 1 , R 2 , R 3 and R 4 The hydrogenation product, where is hydrogen, is obtained in sufficient purity, and further purification steps (e.g., chromatography or distillation) are not usually necessary, but can be applied if a very pure product is desired. For further details of purification methods, see the note below related to step (f).

[0229] R 5 If a compound (I) is obtained in which R is not hydrogen, step (d) is carried out. 5 Etherification (or alkylation) reactions to give compounds in which R is C1-C4-alkyl and 5 -C(=O)-R 6 The esterification (or acylation) reactions to give compounds of the formula: can be carried out according to standard procedures of organic chemistry.

[0230] The above etherification or alkylation reactions can be carried out under conventional alkylation reaction conditions well known in the art. 5 Compound (I) in which R is -C1-C4-alkyl5 is H and R 2 , R 3 or R 4 One of them is R 1 together with R represents a double bond (if step (c) was not performed), or R 1 , R 2 , R 3 and R 4 is hydrogen (if step (c) has been carried out), is reacted with an alkylating agent R 7 -Y(wherein, R 7 is a C1-C4-alkyl group and Y represents a leaving group selected from halogens (e.g. Cl, Br, I), sulfonates (e.g. tosylates, mesylates, triflates or nonaflates) and sulfates (e.g. methylsulfate or ethylsulfate). Examples of alkylating agents are methyl iodide, ethyl iodide, dimethylsulfate and diethylsulfate.

[0231] Suitable bases are typically selected from inorganic bases and organic bases.

[0232] Suitable inorganic bases which may be used in this alkylation reaction are, for example, alkali metal carbonates (such as Li2CO3, Na2CO3, K2CO3 or Cs2CO3), alkali metal hydroxides (such as LiOH, NaOH or KOH), and hydride donors (such as NaH, LiAlH4 or NaBH4).

[0233] Suitable organic bases which may be used in this alkylation reaction are, for example, tertiary amines (such as trimethylamine, triethylamine, tripropylamine, ethyldiisopropylamine, etc.) or basic N-heterocycles (such as morpholine, pyridine, lutidine, DMAP (4-dimethylaminopyridine), DABCO (1,4-diazabicyclo(2.2.2)octane), DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) or DBN (1,5-diazabicyclo[4.3.0]non-5-ene)).

[0234] In particular, NaH is used.

[0235] Instead of using a base, the reaction can alternatively be carried out in the presence of a catalytic Lewis acid, such as zinc chloride.

[0236] If the reaction is carried out in the presence of a base, it is expedient to first mix compound (I') with the base (especially if this is a hydride donor) and only afterwards add the alkylating agent.

[0237] The reaction mixture obtained in the above alkylation reaction is subjected to post-treatment, and R 5 The purification / isolation of the product of formula (I), where is -C1-C4-alkyl [optional step (f)] is carried out in a conventional manner, for example by quenching the reaction mixture to hydrolyze any remaining alkylating agent, followed by an extractive work-up with an organic solvent that is insoluble or only slightly soluble in water and suitable for dissolving the resulting reaction product, such as an open-chain ether (e.g. diethyl ether or methyl-tert-butyl ether), dichloromethane or ethyl acetate; and removing the organic solvent, for example under reduced pressure. The desired product is generally obtained in sufficient purity by utilizing such measures or a combination thereof. However, further purification steps, such as chromatography, distillation or rectification, can be used to obtain extremely pure, R 5 This can be done when a compound of formula (I) in which is -C1-C4-alkyl is desired.

[0238] In general, R 5 -C(=O)-R 6 The ester of formula (I) is 5 is H and R 2 , R 3 Or R 4 One of them is R 1 together represent a double bond (if step (c) was not performed) or R 1 , R 2 , R 3 and R4 is hydrogen (if step (c) has been carried out), and a carboxylic acid R 6 -COOH(where R 6 has one of the meanings defined herein) or its anhydride, such as acetic anhydride or propionic anhydride. This reaction is typically carried out in the presence of an esterification catalyst or a base.

[0239] Suitable esterification catalysts that may be utilized in this reaction are well known in the art, such as metal-based catalysts (e.g., iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides, or metal salts (e.g., metal alkoxylates); mineral acids (e.g., sulfuric acid, hydrochloric acid, or phosphoric acid); or organic sulfonic acids (e.g., methanesulfonic acid, or para-toluenesulfonic acid).

[0240] Suitable bases are, for example, organic bases as defined above (such as, in particular, pyridine, lutidine or DMAP), especially DMAP.

[0241] Or, R 5 -(C=O)-R 6 The ester of formula (I) is 5 is H, and a compound (I') of formula R 6 -(C=O)Y' (where R 6 has one of the meanings defined herein and Y' is a halogen (e.g. Cl, Br or I) with an acid halide in the presence of an organic base (preferably one of the organic bases defined above).

[0242] Preferably, R 5 -(C=O)-R 6 The ester of formula (I) is a compound (I′) (wherein R 5 is H) and carboxylic acid R 6 It is prepared by reacting with an acid anhydride of -COOH in the presence of an organic base.

[0243] As outlined above, R 5 -(C=O)-R 6 The particular reaction conditions for the preparation of esters of formula (I) are well known in the art.

[0244] The reaction mixture obtained in the above acylation reaction is subjected to post-treatment, and R 5 -(C=O)-R 6 The isolation / purification of the product of formula (I), which is [optional step (f)], is carried out in a conventional manner, for example by quenching the reaction mixture to hydrolyze any remaining acid anhydride or acid halide, followed by an extractive work-up with an organic solvent that is insoluble or only slightly soluble in water and suitable for dissolving the resulting reaction product, such as an open-chain ether (e.g. diethyl ether or methyl-tert-butyl ether), dichloromethane or ethyl acetate; and by removing the organic solvent, for example under reduced pressure. The desired product is generally obtained in sufficient purity by utilizing such measures or a combination thereof. However, further purification steps, such as chromatography, distillation or rectification, can be used to obtain the extremely pure, R 5 -(C=O)-R 6 This can be done when a compound of formula (I) which is

[0245] Alternatively, compound (I) can be prepared by subjecting hydroxypivalinaldehyde (2) to an esterification or etherification reaction, followed by reacting the resulting ester / ether with 3-methylbut-3-en-1-ol (isoprenol) (1), as shown in Scheme 2 (Method B) below. The reaction of the ester / ether of (2) (compound (3) in Scheme 2) with (1) is typically carried out in the presence of a BF3 source. The above reaction is carried out to obtain compound (I) (wherein R 5 is different from H) [hereinafter referred to as compound (I''); 5 is below 5a This brings about what is called.

[0246] Scheme 2:

[0247] [ka]

[0248] In the reaction product (I'') of Scheme 2, R 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4 The remainder of are hydrogen, and R 5a is C1-C4-alkyl or -C(=O)-R 6 (where R 6 is as defined above).

[0249] Thus, another aspect of the present invention relates to a compound of formula (I) as defined above, 5 is C1-C4-alkyl and -C(=O)-R 6 A process for preparing a compound (I) or its stereoisomer, a mixture of stereoisomers, a mixture of different compounds (I), comprising the steps of: (i) 3-hydroxy-2,2-dimethyl-propanal (hydroxypivalinaldehyde) is subjected to an etherification reaction or an esterification reaction to obtain a compound represented by formula 3:

[0250] [ka] (In the formula, R 5a is C1-C4-alkyl and -C(=O)-R 6 selected from the group consisting of; obtaining a reaction mixture comprising the compound of formula (I); (ii) optionally isolating the compound of formula 3 from the reaction mixture obtained in step (i) or enriching it in the reaction mixture obtained in step (i); (iii) reacting the reaction mixture obtained in step (i) or the product obtained in step (ii) with 3-methylbut-3-en-1-ol (isoprenol) in the presence of a BF source to obtain a compound of formula (I), 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4 The remainder of are hydrogen, and R 5 is C1-C4-alkyl and -C(=O)-R 6 obtaining a reaction mixture comprising: (iv) a compound of formula (I), 1 , R 2 , R 3 and R 4 is hydrogen, and R 5 is C1-C4-alkyl and -C(=O)-R 6 (selected from the group consisting of): subjecting the product obtained in step (iii) to a hydrogenation reaction; and (v) optionally subjecting the product obtained in step (iii) or step (iv) to a purification step. The present invention relates to the above method, comprising:

[0251] The above etherification or esterification step (i) may be carried out according to standard procedures in organic chemistry, as depicted above for step (d).

[0252] The etherification or alkylation reaction of step (i) above can be carried out under conventional alkylation reaction conditions well known in the art. 5a Compound (3), in which is -C1-C4-alkyl, can be prepared by reacting compound (2) with an alkylating agent R 7 -Y(wherein, R 7is a C1-C4-alkyl group and Y represents a leaving group selected from halogens (e.g. Cl, Br, I), sulfonates (e.g. tosylates, mesylates, triflates or nonaflates) and sulfates (e.g. methyl sulfate or ethyl sulfate). Examples of alkylating agents are methyl iodide, ethyl iodide, dimethyl sulfate, diethyl sulfate, dimethyl carbonate and diethyl carbonate.

[0253] Suitable bases are typically selected from inorganic bases and organic bases.

[0254] Suitable inorganic bases which may be used in this alkylation reaction are, for example, alkali metal carbonates (such as Li2CO3, Na2CO3, K2CO3 or Cs2CO3), alkali metal hydroxides (such as LiOH, NaOH or KOH), and hydride donors (such as NaH, LiAlH4 or NaBH4).

[0255] Suitable organic bases which may be used in this alkylation reaction are, for example, tertiary amines (such as trimethylamine, triethylamine, tripropylamine, ethyldiisopropylamine, etc.) or basic N-heterocycles (such as morpholine, pyridine, lutidine, DMAP (4-dimethylaminopyridine), DABCO (1,4-diazabicyclo(2.2.2)octane), DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) or DBN (1,5-diazabicyclo[4.3.0]non-5-ene)).

[0256] Instead of using a base, the reaction can alternatively be carried out in the presence of a Bronsted or Lewis acid as a catalyst. Suitable Bronsted acids are those listed above in connection with step (a) of method A. A suitable Lewis acid is, for example, zinc chloride.

[0257] When the reaction is carried out in the presence of a base, it is expedient to first mix compound (2) with the base (especially if this is a hydride donor) and only afterwards add the alkylating agent.

[0258] The reaction mixture obtained in the above alkylation reaction is subjected to post-treatment and R 5a The purification / isolation of the product (3) where R is -C1-C4-alkyl [optional step (b)] is carried out in a conventional manner, for example by quenching the reaction mixture to hydrolyze any remaining alkylating agent, followed by an extractive work-up with an organic solvent that is insoluble or only slightly soluble in water and suitable for dissolving the resulting reaction product, such as an open-chain ether (e.g. diethyl ether or methyl-tert-butyl ether), dichloromethane or ethyl acetate; and removing the organic solvent, for example under reduced pressure. The desired product is generally obtained in sufficient purity by utilizing such measures or a combination thereof. However, further purification steps, such as chromatography, distillation or rectification, can be used to obtain extremely pure, R 5a This can be done when a compound of formula 3 in which is -C1-C4-alkyl is desired.

[0259] In general, R 5a -C(=O)-R 6 The ester of formula 3, 6 -COOH(where R 6 has one of the meanings defined herein) or its anhydride, such as acetic anhydride or propionic anhydride. This reaction is typically carried out in the presence of an esterification catalyst or a base.

[0260] Suitable esterification catalysts which may be utilized in this reaction are well known in the art and include, for example, acids such as mineral acids (e.g., sulfuric acid, hydrochloric acid, or phosphoric acid); or organic sulfonic acids (e.g., methanesulfonic acid, para-toluenesulfonic acid, or camphorsulfonic acid); or metal-based catalysts (e.g., iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides, or metal salts (e.g., metal alkoxylates).

[0261] Suitable bases are, for example, organic bases as defined above, such as in particular pyridine, lutidine or DMAP, especially DMAP.

[0262] Or, R 5a -(C=O)-R 6 The ester of formula 3, which is 6 -(C=O)Y' (where R 6 has one of the meanings defined herein and Y' is a halogen (eg, Cl, Br or I) with an acid halide.

[0263] Preferably, R 5a -(C=O)-R 6 The ester of formula 3, which is represented by the formula (3), can be prepared by reacting compound (2) with a carboxylic acid R 6 It is prepared by reacting with -COOH. In particular, toluenesulfonic acid is used.

[0264] The acid is generally used in a catalytic amount, for example, 0.01 to 20 mol %, preferably 0.05 to 15 mol %, particularly 0.1 to 10 mol %, and especially 1 to 5 mol %, per mol of (2).

[0265] As outlined above, R 5a -(C=O)-R 6 The particular reaction conditions for the preparation of esters of formula 3, which are: are well known in the art.

[0266] In the presence of an acid, compound (2) and carboxylic acid R 6 In the preferred embodiment of reacting with -COOH, suitably the water formed in the reaction is removed, typically by distillation, to facilitate the reaction.

[0267] The reaction mixture obtained in the above acylation reaction is subjected to post-treatment, and R 5a -(C=O)-R 6 Isolation / purification of the product of formula 3, where [optional step (b)] is carried out in a conventional manner, for example by chromatography, distillation or rectification, especially if a highly pure compound (3) is desired.

[0268] The reaction of (1) with (3) in step (iii) is preferably carried out using a BF3 source as a catalyst. Suitable BF3 sources are gaseous BF3 and BF3 complexes with dialkyl ethers (e.g. diethyl ether), dicycloalkyl ethers (e.g. dicyclohexyl ether), tetrahydrofuran, phenol, aryl alkyl ethers (e.g. anisole) or aliphatic alcohols. For practical reasons, the use of BF3 complexes is preferred. Among these, BF3 complexes with dialkyl ethers are preferred, in particular BF3 complexes with diethyl ether (BF3-diethyl etherate).

[0269] The above mentioned BF3 sources are preferably used in substoichiometric amounts, for example in an amount of 1 to 50 mol%, preferably 10 to 30 mol%, in particular 15 to 25 mol%, relative to 1 mol of the starting compound (1) or (3) used in a smaller amount. If (1) and (3) are used in equimolar amounts, the above percentages are of course relative to 1 mol of either starting compound.

[0270] (1) and (3) are usually utilized in a molar ratio of 0.7:1 to 1.5:1, preferably 0.9:1 to 1.3:1. For economic reasons, it is advantageous to use (1) in at least equimolar amounts, such that the molar ratio of (1) to (3) is, for example, 1:1 to 1.3:1, and it is even more advantageous to use (1) in a slight excess, such that the molar ratio of (1) to (3) is, for example, 1.1:1 to 1.3:1.

[0271] The reactants can in principle be contacted with each other in any desired order. For example, (1) and (3), optionally dissolved or dispersed in an inert solvent, can be placed first and mixed together. The BF3 source can then be added to the resulting mixture. The BF3 source can be added in one go or can be added gradually, either continuously or in several portions. Alternatively, (1) and the BF3 source, optionally dissolved or dispersed in an inert solvent, can be placed first and (3) can then be added. Alternatively, (3) can first be mixed with the BF3 source and this mixture can then be mixed with (1). As a further alternative, all reactants can be added simultaneously to the reaction vessel.

[0272] In a particular embodiment, (1) and (3) are mixed and dissolved or dispersed in an inert solvent and the BF3 source is added in one portion.

[0273] The reaction temperature in step (iii) depends on various factors, for example on the type of BF3 source used (reactions with gaseous BF3 are generally carried out at lower temperatures than with BF3 complexes) and can be determined in each individual case by the skilled person, for example by simple preliminary tests. In general, the conversion in step (iii) is carried out at a temperature in the range of 20-150°C, preferably in the range of 50-130°C, more preferably in the range of 60-100°C.

[0274] After completion of step (iii), compound (I'') is isolated by a conventional work-up, for example by treating the resulting reaction mixture with an aqueous base, such as aqueous sodium bicarbonate. The organic phase containing compound (I'') can then be separated from the aqueous phase and concentrated to obtain compound (I'').

[0275] R 1 , R 2 , R 3 and R 4 The product of step (iii) is subjected to a hydrogenation reaction [step (iv)] to obtain compound (I), in which is hydrogen. Suitable hydrogenation conditions correspond to those described above for steps (c) and (e) of method A.

[0276] In an optional step (v) following step (iii) or (iv), the crude product obtained in step (iii) or (iv) may be subjected to a further purification step, such as distillation or chromatography, in particular distillation.

[0277] Step (iii) generally involves the conversion of at least two of the three double bond isomers (I-1), (I-2) and (I-3), most frequently (I-1), (I-2) and (I-3) (wherein R 5 is C1-C4-alkyl or -C(=O)-R 6 This produces a mixture containing all three of the double bond isomers (wherein n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 109, 109, 109, 110, 111, 112, 113, 114, 115, 116, 117,

[0278] Method B is R 5 is C1-C4-alkyl or -C(=O)-R 6 The compound (I) is produced.

[0279] Method B generally avoids the formation of acetal compounds (II.1) and (II.2).

[0280] Another aspect of the invention is a product obtainable by the process of the invention (Process A or Process B).

[0281] Uses and methods of using compound (I) As already explained, the compounds of formula (I) as defined above, or a stereoisomer thereof, or a mixture of two or more stereoisomers thereof, or a mixture of two or more different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), are useful as aroma chemicals.

[0282] Thus, a further aspect of the present invention is the use, as an aroma chemical, of a compound of formula (I) as defined above, or of a stereoisomer thereof, or of a mixture of two or more stereoisomers thereof, or of a mixture of two or more different compounds (I), or of a mixture of at least one compound of formula (I) with one or both of the compounds of formulae (II.1) and / or (II.2).

[0283] Preferably, the compounds of formula (I) as defined above, or their stereoisomers, or a mixture of two or more of its stereoisomers, or a mixture of two or more different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), are used to impart an olfactory impression. In particular, the compounds of formula (I) as defined above, or their stereoisomers, or a mixture of two or more of its stereoisomers, or a mixture of two or more different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), are used as fragrances.

[0284] In particular, mixtures of the above compounds (I-1), (I-2) and (I-3) (wherein in each case R 5is H) are used to impart pineapple, green and chrysanthemum notes; or to produce odors having pineapple, green and chrysanthemum notes. In particular, compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is H) are present in a weight ratio of about 40:25:35.

[0285] In particular, mixtures of the above compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH3) are used to impart floral, apricot, green or bux tree notes; or to produce odors having floral, apricot, green or bux tree notes. In particular, compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH3) are present in a weight ratio of approximately 70:15:15.

[0286] In particular, mixtures of the above compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH3) are used to impart sweet, woody, green or herbal notes; or to produce aromas having sweet, woody, green or herbal notes. In particular, compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH3) are present in a weight ratio of about 44:18:33 or about 2:66:30.

[0287] In particular, mixtures of the abovementioned compounds (I-1), (I-3), (II.1) and (II.2), in each case R 5 is -C(=O)CH2CH3) are used to impart a white floral note, a freesia note, a grape note; or to produce a fragrance having a white floral note, a freesia note, a grape note. In particular, the compounds (I-1), (I-3), (II.1) and (II.2) (wherein in each case R 5 is -C(=O)CH2CH3) are present in a weight ratio of approximately 50:20:20:5.

[0288] In particular, mixtures of the above compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH2CH3) are used to impart woody, ambery, peppery, natural, warm or spicy notes; or to produce aromas having woody, ambery, peppery, natural, warm or spicy notes. In particular, compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH2CH3) are present in a weight ratio of approximately 52:23:19.

[0289] In particular, mixtures of the above compounds (I-1), (I-2) and (I-3) (wherein in each case R 5is -C(=O)CH2CH3) are used to impart cedarwood notes, smoky notes, dusty notes; or to produce odors having cedarwood notes, smoky notes, dusty notes. In particular, compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH2CH3) are present in a weight ratio of approximately 2:62:35.

[0290] In particular, mixtures of the above compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -CH3) are used to impart floral, pencil shavings, carrot, lime, bergamot notes; or to produce fragrances having floral, pencil shavings, carrot, lime, bergamot notes. In particular, compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH3) are present in a weight ratio of approximately 35:45:20.

[0291] In particular, mixtures of the above compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -CH2CH3) are used to impart etheral, herbal, soapy, mimosa, cedarwood, floral notes; or to produce odors having etheral, herbal, soapy, mimosa, cedarwood, floral notes. In particular, compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -CH2CH3) are present in a weight ratio of approximately 50:30:20.

[0292] Compound (I), mixtures thereof, stereoisomers thereof, stereoisomeric mixtures thereof or mixtures of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) are generally used in ready-to-use compositions, in particular in fragranced ready-to-use compositions. As used herein, "fragranced ready-to-use composition" refers to a ready-to-use composition that induces a predominantly pleasant odor impression.

[0293] Fragranced ready-to-use compositions are, for example, compositions used in personal care, compositions used in home care, compositions used in industrial applications as well as compositions used in other applications (e.g. pharmaceutical compositions or crop protection compositions).

[0294] Preferably, the compound of formula (I), or a stereoisomer thereof, or a mixture of two or more stereoisomers thereof, or a mixture of two or more different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), is used in a composition selected from the group consisting of perfume compositions, body care compositions (including cosmetic compositions), oral and dental hygiene products, hygiene articles, cleaning compositions (including dishwashing compositions), fabric detergent compositions, compositions for fragrance dispensers, food products, dietary supplements, pharmaceutical compositions, and crop protection compositions.

[0295] In particular, the above compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is H) is used to impart pineapple, green and chrysanthemum notes to the compositions listed above. In particular, the compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is H) are present in a weight ratio of about 40:25:35.

[0296] In particular, mixtures of the above compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH3) are used to impart floral, apricot, green and buckthorn notes to the compositions listed above. In particular, compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH3) are present in a weight ratio of approximately 70:15:15.

[0297] In particular, mixtures of the above compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH3) are used to impart sweet, woody, green and herbal notes to the compositions listed above. In particular, compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH3) are present in a weight ratio of about 44:18:33 or about 2:66:30.

[0298] In particular, mixtures of the abovementioned compounds (I-1), (I-3), (II.1) and (II.2), in each case R 5 is -C(=O)CH2CH3) are used to impart white floral, freesia and grape notes to the compositions listed above. In particular, compounds (I-1), (I-3), (II.1) and (II.2) (wherein R in each case is 5 is -C(=O)CH2CH3) are present in a weight ratio of approximately 50:20:20:5.

[0299] In particular, mixtures of the above compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH2CH3) are used to impart woody, ambery, peppery, natural, warm and spicy notes to the compositions listed above. In particular, compounds (I-1), (I-2) and (I-3) (wherein in each case R5 is -C(=O)CH2CH3) are present in a weight ratio of approximately 52:23:19.

[0300] In particular, mixtures of the above compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -C(=O)CH2CH3) are used to impart cedarwood, smoky and dusty notes to the compositions listed above. In particular, compounds (I-1), (I-2) and (I-3) (wherein R 5 is -C(=O)CH2CH3) are present in a weight ratio of approximately 2:62:35.

[0301] In particular, mixtures of the above compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -CH3) are used to impart floral, pencil shaving, carrot, lime and bergamot notes to the compositions listed above. In particular, compounds (I-1), (I-2) and (I-3) (wherein in each case R 5 is -CH3) are present in a weight ratio of approximately 35:45:20.

[0302] In particular, in both cases R 5 The mixture of the above compounds (I-1), (I-2) and (I-3), in which R is -CH2CH3, is used to impart ethereal, herbal, soapy, mimosa, cedarwood and floral notes to the compositions listed above. In particular, the compounds (I-1), (I-2) and (I-3), in each case R 5 is -CH2CH3) are present in a weight ratio of approximately 50:30:20.

[0303] Details regarding the above listed compositions are provided below.

[0304] In addition to the olfactory properties, compound (I), mixtures thereof, stereoisomers thereof, stereoisomeric mixtures thereof or mixtures of at least one compound of formula (I) with one or both of the compounds of formulae (II.1) and / or (II.2) exhibit advantageous secondary properties.

[0305] For example, they may provide a better sensory profile as a result of synergy with other fragrances, which means that they may provide a booster effect to other fragrances, and therefore they are suitable as boosters for other fragrances.

[0306] Another aspect of the present invention therefore relates to the use of compound (I), a mixture thereof, a stereoisomer thereof, a mixture of stereoisomers thereof or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) for modifying the odour characteristics of a fragranced composition; also in particular the use as a booster agent for other fragrances.

[0307] The booster effect means that the substance enhances and strengthens the overall impression of the mixture in a perfume formulation. For example, in the mint range, it is known that menthyl methyl ether enhances the perfume or taste mixture of peppermint oil, resulting in a significantly stronger and more complex perception, especially in the top note, even though the pure substance, the ether, does not produce any particular strong odor by itself. In fragrance applications, Hedione® (methyl dihydrojasmonate) only exhibits a light floral jasmine note as a pure substance, but as an odor booster, it enhances the diffusion, freshness and volume of the perfume composition. The booster effect is particularly desirable when applications are required that are characterized by a top note in which the odor impression is particularly quickly and strongly transmitted, for example in deodorants, in air fresheners, or in the taste category, in chewing gum.

[0308] To achieve such a booster effect, compound (I), a mixture thereof, a stereoisomer thereof or a mixture of stereoisomers thereof is generally used in an amount of 0.1 to 20% by weight, preferably in an amount of 0.5 to 5% by weight and in particular in an amount of 0.6 to 3% by weight, relative to the total weight of the fragrance mixture.

[0309] Additionally, compound (I), mixtures thereof, stereoisomers thereof, or mixtures of stereoisomers thereof may have additional beneficial effects on the compositions in which they are used, for example, they may enhance the overall performance of the compositions in which they are incorporated, such as the stability (e.g., formulation stability), extendibility or durability of the composition.

[0310] A further embodiment of the present invention is directed to a method for preparing an aroma chemical composition, in particular a fragranced composition, especially a fragranced ready-to-use composition, comprising incorporating at least one compound of formula (I), its stereoisomer, or a mixture of its stereoisomers, into a target composition, such as a ready-to-use composition, resulting in an aroma chemical composition, in particular a fragranced composition, especially a fragranced ready-to-use composition. Alternatively, the present invention is directed to a method for preparing an aroma chemical composition, in particular a fragranced composition, especially a fragranced ready-to-use composition, comprising mixing at least one compound of formula (I), its stereoisomer, or a mixture of its stereoisomers, with at least one aroma chemical different from compound (I), and / or with at least one non-aroma chemical carrier, and / or with at least one antioxidant, and / or with at least one deodorising active. Suitable and preferred fragrance chemicals different from compound (I), non-fragrance chemical carriers, antioxidants and deodorizing actives are described below.

[0311] For example, the above method can be carried out by mixing at least one compound of formula (I) as defined above, its stereoisomer, or a mixture of its stereoisomers with at least one further ingredient selected from the group consisting of fragrance chemicals different from compound (I), non-fragrance chemical carriers, antioxidants and deodorising actives.

[0312] The present invention is also directed to a method for modifying the odor characteristics of an aroma chemical composition, in particular a fragranced composition, especially a fragranced ready-to-use composition, which method comprises incorporating at least one compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) into the aroma chemical composition, in particular into the fragranced composition, especially into the fragranced ready-to-use composition.

[0313] In particular, the present invention is directed to a method for preparing a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food, a dietary supplement, a pharmaceutical composition or a crop protection composition, comprising including a compound of formula (I) as defined above, a mixture thereof, a stereoisomer thereof, a mixture of stereoisomers thereof or a mixture of at least one compound of formula (I) with one or both of the compounds of formulae (II.1) and / or (II.2) in the perfume composition, the body care composition, the oral and dental hygiene product, the hygiene article, the cleaning composition, the fabric detergent composition, the composition for a scent dispenser, a food, a dietary supplement, a pharmaceutical composition or a crop protection composition.

[0314] In a particular embodiment, the present invention relates to a method for imparting pineapple notes, green notes, chrysanthemum notes to perfume compositions, body care compositions, oral and dental hygiene products, hygiene articles, cleaning compositions, fabric detergent compositions, compositions for scent dispensers, foods, dietary supplements, pharmaceutical compositions or crop protection compositions, comprising the steps of: 5 is H), or a mixture of stereoisomers thereof, in a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food, a dietary supplement, a pharmaceutical composition or a crop protection composition. 5 is H) are present in a weight ratio of about 40:25:35.

[0315] In a particular embodiment, the present invention relates to a method for imparting floral, apricot, green or buckthorn notes to a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food product, a dietary supplement, a pharmaceutical composition or a crop protection composition, comprising the steps of: 5 is -C(=O)CH3), or a mixture of stereoisomers thereof, in a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food, a dietary supplement, a pharmaceutical composition or a crop protection composition. 5 is -C(=O)CH3) are present in a weight ratio of approximately 70:15:15.

[0316] In a particular embodiment, the present invention relates to a method for imparting sweet, woody, green or herbal notes to a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food product, a dietary supplement, a pharmaceutical composition or a crop protection composition, comprising the steps of: 5 is -C(=O)CH3), or a mixture of stereoisomers thereof, in a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food, a dietary supplement, a pharmaceutical composition or a crop protection composition. 5 is -C(=O)CH3) are present in a weight ratio of about 44:18:33 or 2:66:30.

[0317] In another particular embodiment, the present invention relates to a method for imparting white floral notes, freesia notes, grape notes to a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food product, a dietary supplement, a pharmaceutical composition or a crop protection composition, comprising the steps of: 5 is -C(=O)CH2CH3), or a mixture of stereoisomers thereof, in a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food, a dietary supplement, a pharmaceutical composition or a crop protection composition. 5 is -C(=O)CH2CH3) are present in a weight ratio of approximately 50:20:20:5.

[0318] In another particular embodiment, the present invention relates to a method for imparting woody, ambery, peppery, natural, warm or spicy notes to a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food product, a dietary supplement, a pharmaceutical composition or a crop protection composition, comprising the steps of: 5 is -C(=O)CH2CH3), or a mixture of stereoisomers thereof, in a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food, a dietary supplement, a pharmaceutical composition or a crop protection composition. 5 is -C(=O)CH2CH3) are present in a weight ratio of approximately 52:23:19.

[0319] In another particular embodiment, the present invention relates to a method for imparting cedarwood, smoky or dusty notes to a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food product, a dietary supplement, a pharmaceutical composition or a crop protection composition, comprising the steps of: 5 is -C(=O)CH2CH3), or a mixture of its stereoisomers, in a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food, a dietary supplement, a pharmaceutical composition or a crop protection composition. 5 is -C(=O)CH2CH3) are present in a weight ratio of approximately 2:62:35.

[0320] In another particular embodiment, the present invention relates to a method for imparting floral notes, pencil shaving notes, carrot notes, lime notes, bergamot notes to perfume compositions, body care compositions, oral and dental hygiene products, hygiene articles, cleaning compositions, fabric detergent compositions, compositions for scent dispensers, foods, dietary supplements, pharmaceutical compositions or crop protection compositions, comprising the steps of: 5 is -CH3), or a mixture of stereoisomers thereof, in a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food, a dietary supplement, a pharmaceutical composition or a crop protection composition. 5 is -CH3) are present in a weight ratio of approximately 35:45:20.

[0321] In another particular embodiment, the present invention relates to a method for imparting ethereal, herbal, soapy, mimosa, cedarwood, floral notes to a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food product, a dietary supplement, a pharmaceutical composition or a crop protection composition, comprising the steps of: 5 is -CH3), or a mixture of its stereoisomers in a perfume composition, a body care composition, an oral and dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a scent dispenser, a food, a dietary supplement, a pharmaceutical composition or a crop protection composition. 5 is -CH3) are present in a weight ratio of approximately 50:30:20.

[0322] composition The present invention further relates to a composition comprising a compound of formula (I) as defined above, a mixture thereof [i.e. a mixture of different compounds (I)], a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one further ingredient selected from the group consisting of aroma chemicals different from compounds (I), (II.1) and (II.2), non-aroma chemical carriers, antioxidants and deodorising actives.

[0323] The above (further) aroma chemicals are of course different from the compounds of formulae (I), (II.1) and (II.2), or their stereoisomers, or mixtures of their stereoisomers.

[0324] The non-fragrance chemical carriers are in particular selected from the group consisting of surfactants, oil components (emollients) and solvents.

[0325] Thus, in a preferred embodiment, the composition comprises a compound of formula (I) as defined above, a mixture thereof [i.e. a mixture of different compounds (I)], a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one further ingredient selected from the group consisting of aroma chemicals different from compounds (I), (II.1) and (II.2), surfactants, oil components, solvents, antioxidants and deodorising actives. Its pleasant odour, low volatility and good solubility make compound (I) a suitable ingredient in compositions where a pleasant odour is desired.

[0326] Thus, said composition is preferably an aromachemical composition, more preferably an odorant composition, and especially a fragrance composition.

[0327] One embodiment of the present invention is directed to a composition comprising a compound of formula (I) as defined above, a mixture thereof [i.e. a mixture of different compounds (I)], a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one further component selected from the group consisting of an oil component, a solvent, an antioxidant and a deodorising active.

[0328] One embodiment of the present invention is directed to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one aroma chemical.

[0329] One embodiment of the present invention is directed to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one non-aroma chemical carrier.

[0330] One embodiment of the present invention is directed to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one surfactant.

[0331] One embodiment of the present invention is directed to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one oil component.

[0332] One embodiment of the present invention is directed to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one solvent.

[0333] One embodiment of the present invention is directed to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one antioxidant.

[0334] One embodiment of the present invention is directed to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one deodorising active.

[0335] The compounds of formula (I), their stereoisomers, mixtures of their stereoisomers, mixtures of different compounds (I) or mixtures of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) can preferably be used in fragrance compositions. In a preferred embodiment, the fragrance composition is an odor composition, i.e. a composition which induces an odor impression, in particular a fragrance composition, i.e. a composition which induces a pleasant odor.

[0336] The compositions according to the present invention are selected from the group consisting of, but not limited to, perfume compositions, body care compositions (including cosmetic compositions), oral and dental hygiene products, hygiene articles, cleaning compositions (including dishwashing compositions), fabric detergent compositions, fragrance dispenser compositions, food products, dietary supplements, pharmaceutical compositions and crop protection compositions.

[0337] Aroma chemicals (different from compound (I)) Due to the physical properties of compound (I), said combination of compounds has particularly good and practically universal solvent properties for and in aroma chemicals and other conventional ingredients in aroma compositions, such as fragrance compositions.Thus, the compound of formula (I), its stereoisomers, mixtures of its stereoisomers, mixtures of different compounds (I), or mixtures of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) can be successfully combined with aroma chemicals (including their stereoisomers) different from compounds (I), (II.1) and (II.2), in particular allowing the creation of aroma compositions (preferably fragrance compositions) with novel and advantageous sensory profiles.In particular, as already explained above, this combination can boost the sensory profile (e.g. of fragrances) of aroma chemicals (said aroma chemicals different from compounds (I), (II.1) and (II.2)).

[0338] The compositions of the present invention may comprise at least one aroma chemical different from compounds (I), (II.1) and (II.2). The at least one aroma chemical may be, for example, 1, 2, 3, 4, 5, 6, 7, 8 or even more aroma chemicals selected from the group consisting of:

[0339] Geranyl acetate (3,7-dimethyl-2,6-octadien-1yl acetate), α-hexylcinnamaldehyde, 2-phenoxyethyl isobutyrate (Phenirat 1 ), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), methyl dihydrojasmonate (preferably with a content of cis isomer of more than 60% by weight) (Hedione 9 , Hedione HC 9 ), 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydro-cyclopenta[g]benzopyran (Galaxolid 3), Tetrahydrolinalool (3,7-dimethyloctan-3-ol), Ethyl linalool, Benzyl salicylate, 2-Methyl-3-(4-tert-butylphenyl)propanal (Lysmeral 2 ), 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 (Herbaflorat 1 ), citronellol, citronellyl acetate, tetrahydrogeraniol, vanillin, linalyl acetate, styrolyl acetate (1-phenylethyl acetate), octahydro-2,3,8,8-tetramethyl-2-acetonaphthone and / or 2-acetyl-1,2,3,4,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene (Iso E Super 3 ), Hexyl Salicylate, 4-tert-Butylcyclohexyl Acetate (Oryclone 1 ), 2-tert-butylcyclohexyl acetate (Agrumex HC 1 ), α-ionone (4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one), n-α-methyl ionone, α-isomethyl ionone, coumarin, terpinyl acetate, 2-phenylethyl alcohol, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene carboxaldehyde (Lyral 3 ), α-amylcinnamaldehyde, ethylene brassylate, (E)- and / or (Z)-3-methylcyclopentadec-5-enone (Muscenon 9 ), 15-pentadec-11-enolide and / or 15-pentadec-12-enolide (Globalide 1 ), 15-Cyclopentadecanolide (Macrolide 1 ), 1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthalenyl)ethanone (Tonalid 10 ), 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol (Florol 9), 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol (Sandolen 1 ), cis-3-hexenyl acetate, trans-3-hexenyl acetate, trans-2 / cis-6-nonadienol, 2,4-dimethyl-3-cyclohexenecarboxaldehyde (Vertocitral 1 ), 2,4,4,7-tetramethyloct-6-en-3-one (Claritone 1 ), 2,6-Dimethyl-5-hepten-1-al (Melonal 2 ), borneol, 3-(3-isopropylphenyl)butanal (Florhydral 2 ), 2-methyl-3-(3,4-methylenedioxyphenyl)propanal (Helional 3 ), 3-(4-ethylphenyl)-2,2-dimethylpropanal (Florazon 1 ), 7-methyl-2H-1,5-benzodioxepin-3(4H)-one (Calone), 3,3,5-trimethylcyclohexyl acetate (preferably with a content of cis isomer of 70% or more by weight), 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydronaphthalen-2-ol (Ambrinol S 1 ), 3-(4-tert-butylphenyl)-propanal (Bourgeonal 4 ), Ethyl 2-methylpentanoate (Manzanate 4 ), ethoxymethoxycyclododecane (Amberwood 1 ), 2,4-dimethyl-4,4a,5,9b-tetrahydroindeno[1,2-d][1,3]dioxin (Magnolan 1 ), (2-tert-butylcyclohexyl) acetate (Verdox 3 ) and 3-[5,5,6-trimethylbicyclo[2.2.1]hept-2-yl]cyclohexan-1-ol (Sandela 4). Thus, within the context of the present invention, the above mentioned aroma chemical(s) are preferably combined with a compound of formula (I) above, a stereoisomer thereof, a mixture of stereoisomers thereof or a mixture of different compounds (I).

[0340] Where trade names are given above, these refer to the following sources: 1 Product name of Symrise GmbH (Germany), 2 BASF SE product name, 3 Product name of International Flavorss & Fragrances Inc., USA (USA) 4 Givaudan AG (Switzerland), 9 Product name of Firmenich SA (Switzerland) 10 PFW Trade name of Aroma Chemicals BV (Netherlands).

[0341] A preferred embodiment of the present invention relates to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one aroma chemical selected from the group consisting of methyl benzoate, benzyl acetate, geranyl acetate, 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol and linalool.

[0342] Further embodiments of the present invention relate to compositions comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol.

[0343] A further embodiment of the present invention relates to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and methyl benzoate.

[0344] A preferred embodiment of the present invention relates to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I) or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) and at least one further aroma chemical selected from the group consisting of ethyl vanillin, vanillin, 2,5-dimethyl-4-hydroxy-2H-furan-3-one (furaneol) or 3-hydroxy-2-methyl-4H-pyran-4-one (maltol).

[0345] Further fragrance chemicals that may be combined with the above compounds of formula (I), their stereoisomers, mixtures of their stereoisomers, mixtures of different compounds (I) or mixtures of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) to give compositions according to the invention can be found, for example, in the self-published books S. Arctander, Perfume and Flavor Chemicals, Vol. I and II, Montclair, NJ, 1969, or K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4th Edition, Wiley- VCH, Weinheim 2001. In particular, the following may be mentioned:

[0346] Extracts derived from natural sources, such as essential oils, concretes, absolutes, resins, resinoids, balsams, tinctures, e.g. Ambergris tincture, Amyris oil, Angelica seed oil, Angelica root oil, Anise oil, Valerian oil, Basil oil, Tree moss absolute, Bay oil, Artemisia oil, Benzoin resin, Bergamot oil, Beeswax absolute, Birch tar oil, Bitter almond oil, Savory oil, Bouquet leaf oil, Cabreuba oil, Cade oil, Calmus oil, Camphor oil, Cananga oil, Cardamom oil, Cascarilla oil, Cassia oil, Cassia absolute, Castorium absolute, Cedar leaf oil, Cedarwood 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 oeuvre brouts) absolute, oakmoss absolute, elemi oil, tarragon oil, eucalyptus citriodora (eucalyptus citriodora oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, galbanum resin, geranium oil, grapefruit oil, guaiac wood oil, gharjan balsam, gharjan balsam oil, helichrysum absolute, helichrysum oil, ginger oil, iris root absolute, iris root oil, jasmine absolute, calamus oil, blue chamomile oil, 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, distilled lime oil, pressed lime oil, linalool oil, litseacubeba) 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, clove leaf oil, clove flower oil, neroli oil, frankincense absolute, frankincense oil, opopanax oil, orange flower absolute, orange oil, origanum oil, palmarosa oil, patchouli oil, perilla oil, pelargonium oil, parsley leaf oil, parsley seed oil, petitgrain oil, peppermint oil, cocos malt oil, pimento oil, pine oil, pennyroyal oil, rose absolute, rosewood 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 leaf oil, tea tree oil, turpentine oil, thyme oil, tolu balsam, tonka absolute, tuberose absolute, vanilla extract, violet leaf absolute, verbena oil, vetiver oil, juniper berry oil, wine lees oil, wormwood oil, wintergreen oil, hyssop oil, civet absolute, cinnamon leaf oil, cinnamon bark oil, and fractions thereof or components isolated therefrom. Individual fragrances from the group of hydrocarbons, such as 3-carene, α-pinene, β-pinene, α-terpinene, γ-terpinene, p-cymene, bisabolene, camphene, caryophyllene, cedrene, farnesene, limonene, longifolene, myrcene, ocimene, valencene, (E,Z)-1,3,5-undecatriene, styrene, diphenylmethane, etc. Aliphatic alcohols, such as 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, a 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, etc. Aliphatic aldehydes and their acetals, such as 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 diethyl acetal, 1,1-dimethoxy-2,2,5-trimethyl-4-hexene, citronellyloxyacetaldehyde, (E / Z)-1-(1-methoxypropoxy)-hex-3-ene, etc., aliphatic ketones and their oximes, such as 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, etc. Aliphatic sulfur-containing compounds, such as 3-methylthiohexanol, 3-methylthiohexyl acetate, 3-mercaptohexanol, 3-mercaptohexyl acetate, 3-mercaptohexyl butyrate, 3-acetylthiohexyl acetate, 1-menthene-8-thiol, etc. Aliphatic nitriles, such as 2-nonenenitrile, 2-undecenenitrile, 2-tridecenenitrile, 3,12-tridecadienonitrile, 3,7-dimethyl-2,6-octadienenitrile, 3,7-dimethyl-6-octenenitrile, etc. Esters of aliphatic carboxylic acids, such as (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, 1-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-isoamyloxyacetate, methyl-3,7-dimethyl-2,6-octadienoate, 4-methyl-2-pentyl crotonate, etc. Acyclic terpene alcohols, such as geraniol, nerol, linalool, lavandulol, nerolidol, farnesol, tetrahydrolinalool, 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-1,5,7-octatrien-3-ol, 2,6-dimethyl-2,5,7-octatrien-1-ol, and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates, and 3-methyl-2-butenoates, Acyclic terpene aldehydes and ketones, such as geranial, neral, citronellal, 7-hydroxy-3,7-dimethyloctanal, 7-methoxy-3,7-dimethyloctanal, 2,6,10-trimethyl-9-undecenal, geranyl acetone, and the dimethyl acetals and diethyl acetals of geranial, neral, and 7-hydroxy-3,7-dimethyloctanal; cyclic terpene alcohols, such as menthol, isopulegol, α-tert-butyl ether, methyl ... Pineol, terpin-4-ol, menthan-8-ol, menthan-1-ol, menthan-7-ol, borneol, isoborneol, linalool oxide, nopol, cedrol, ambrinol, vetiverol, guajol, and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates, and 3-methyl-2-butenoates, etc. Cyclic terpene aldehydes and ketones, such as menthone, isomenthone, 8-mercaptomenthan-3-one, carvone, camphor, fenchone, α-ionone, β-ionone, α-n-methylionone, β-n-methylionone, α-isomethylionone, β-isomethylionone, α-irone, α-damascone, β-damascone, β-damascenone, δ-damascone, γ-damascone, 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-(2-methyl-1,2-dihydro-2-phenyl-2-propanediol), ... )-2-buten-1-one, 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one, 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, nootkatone, dihydronootkatone, 4,6,8-megastigmatrien-3-one, α-sinensal, β-sinensal, acetylated cedarwood oil (methyl cedryl ketone), etc. Cyclic alcohols, such as 4-tert-butylcyclohexanol, 3,3,5-trimethylcyclohexanol, 3-isocamphylcyclohexanol, 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol, 2-isobutyl-4-methyl-tetrahydro-2H-pyran-4-ol, etc. Alicyclic alcohols, such as α-3,3-trimethylcyclohexylmethanol, 1-(4-isopropylcyclohexyl)ethanol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol, 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-1-yl)pentan-2-ol, 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol, 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol, 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol, 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol, etc. Cyclic and alicyclic ethers, such as cineole, cedryl methyl ether, cyclododecyl methyl ether, 1,1-dimethoxycyclododecane, (ethoxymethoxy)cyclododecane, α-cedrene epoxide, 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1-b]furan, 1,5,9-trimethyl-13-oxabicyclo-[10.1.0]trideca-4,8-diene, rose oxide, 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane, etc. Cyclic and macrocyclic ketones, such as 4-tert-butylcyclohexanone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-heptylcyclopentanone, 2-pentylcyclopentanone, 2-hydroxy-3-methyl-2-cyclopenten-1-one, 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one, 3-methyl-2-pentyl-2-cyclopenten-1-one, 3-methyl-4-cyclopentadecenone, 3-methyl-5-cyclopentadecenone, 3 -Methylcyclopentadecanone, 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone, 4-tert-pentylcyclohexanone, 5-cyclohexadecen-1-one, 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, 8-cyclohexadecen-1-one, 7-cyclohexadecen-1-one, (7 / 8)-cyclohexadecen-1-one, 9-cycloheptadecen-1-one, cyclopentadecanone, cyclohexadecanone, etc. Alicyclic aldehydes, such as 2,4-dimethyl-3-cyclohexenecarbaldehyde, 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde, 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde, etc. Alicyclic ketones, such as 1-(3,3-dimethylcyclohexyl)-4-penten-1-one, 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one, 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone, methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone, tert-butyl(2,4-dimethyl-3-cyclohexen-1-yl)ketone, etc. Esters of cyclic alcohols, such as 2-tert-butylcyclohexyl acetate, 4-tert-butylcyclohexyl 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, etc. Esters of alicyclic alcohols, such as 1-cyclohexylethyl crotonate, Esters of alicyclic carboxylic acids, such as 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-cyclohexenecarboxylate, ethyl 2-methyl-1,3-dioxolane-2-acetate, and the like; Aromatic aliphatic alcohols, such as 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-dimethyl-2-phenylethyl alcohol, 1,1-dimethyl-3-phenylpropanol, 1-ethyl-1-methyl-3-phenylpropanol, 2-methyl-5-phenylpentanol, 3-methyl-5-phenylpentanol, 3-phenyl-2-propen-1-ol, 4-methoxybenzyl alcohol, 1-(4-isopropylphenyl)ethanol, etc. Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, such as benzyl acetate, benzyl propionate, benzyl isobutyrate, benzyl isovalerate, 2-phenylethyl acetate, 2-phenylethyl propionate, 2-phenylethyl isobutyrate, 2-phenylethyl isovalerate, 1-phenylethyl acetate, α-trichloromethylbenzyl acetate, α,α-dimethylphenylethyl acetate, α,α-dimethylphenylethyl butyrate, cinnamyl acetate, 2-phenoxyethyl isobutyrate, 4-methoxybenzyl acetate, etc. Aromatic aliphatic ethers, such as 2-phenylethyl methyl ether, 2-phenylethyl isoamyl ether, 2-phenylethyl 1-ethoxyethyl ether, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, hydroatropaldehyde dimethyl acetal, phenylacetaldehyde glycerol acetal, 2,4,6-trimethyl-4-phenyl-1,3-dioxane, 4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxine, 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxine, etc. Aromatic and araliphatic aldehydes, such as benzaldehyde, phenylacetaldehyde, 3-phenylpropanal, hydroatropaldehyde, 4-methylbenzaldehyde, 4-methylphenylacetaldehyde, 3-(4-ethylphenyl)-2,2-dimethylpropanal, 2-methyl-3-(4-isopropylphenyl)propanal, 2-methyl-3-(4-tert-butylphenyl)propanal, 2-methyl-3-(4-isobutylphenyl)propanal, 3-(4-tert-butylphenyl)propanal; Cinnamaldehyde, α-butylcinnamaldehyde, α-amylcinnamaldehyde, α-hexylcinnamaldehyde, 3-methyl-5-phenylpentanal, 4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 4-hydroxy-3-ethoxybenzaldehyde, 3,4-methylenedioxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 2-methyl-3-(4-methoxyphenyl)propanal, 2-methyl-3-(4-methylenedioxyphenyl)propanal, etc. Aromatic and araliphatic ketones, such as acetophenone, 4-methylacetophenone, 4-methoxyacetophenone, 4-tert-butyl-2,6-dimethylacetophenone, 4-phenyl-2-butanone, 4-(4-hydroxyphenyl)-2-butanone, 1-(2-naphthalenyl)ethanone, 2-benzofuranylethanone, (3-methyl-2-benzofuranyl)ethanone, benzophenone, 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone, 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone, 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone, 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-acetonaphthone, etc. Aromatic and araliphatic carboxylic acids and their esters, such as benzoic acid, phenylacetic acid, methyl benzoate, ethyl benzoate, hexyl benzoate, benzyl benzoate, methyl phenyl acetate, ethyl phenyl acetate, geranyl phenyl acetate, phenylethyl phenyl acetate, methyl cinnamate, ethyl cinnamate, benzyl cinnamate, phenylethyl cinnamate, cinnamyl cinnamate, allyl phenoxy acetate, 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, etc. Nitrogen-containing aromatic compounds, such as 2,4,6-trinitro-1,3-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-methyl anthranilate, Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde, 6-isopropylquinoline, 6-isobutylquinoline, 6-sec-butylquinoline, 2-(3-phenylpropyl)pyridine, indole, skatole, 2-methoxy-3-isopropylpyrazine, 2-isobutyl-3-methoxypyrazine, etc. Phenols, phenyl ethers and phenyl esters, such as estragole, anethole, eugenol, eugenyl methyl ether, isoeugenol, isoeugenyl methyl ether, thymol, carvacrol, diphenyl ether, β-naphthyl methyl ether, β-naphthyl ethyl ether, β-naphthyl isobutyl ether, 1,4-dimethoxybenzene, eugenyl acetate, 2-methoxy-4-methylphenol, 2-ethoxy-5-(1-propenyl)phenol, p-cresyl phenyl acetate, etc. Heterocyclic compounds, such as 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, etc. Lactones, for example 1,4-octanolide, 3-methyl-1,4-octanolide, 1,4-nonanolide, 1,4-decanolide, 8-decen-1,4-olide, 1,4-undecanolide, 1,4-dodecanolide, 1,5-decanolide, 1,5-dodecanolide, 4-methyl-1,4-decanolide, 1,15-pentadecanolide, cis- and trans-11-pentadecanolide, cis- and trans- 12-pentadecen-1,15-olide, 1,16-hexadecanolide, 9-hexadecen-1,16-olide, 10-oxa-1,16-hexadecanolide, 11-oxa-1,16-hexadecanolide, 12-oxa-1,16-hexadecanolide, ethylene 1,12-dodecanedioate, ethylene 1,13-tridecanedioate, coumarin, 2,3-dihydrocoumarin, octahydrocoumarin, and the like.

[0347] Non-fragrance Chemical Carriers A further embodiment of the present invention is directed to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of different compounds (I), and at least one non-aroma chemical carrier.

[0348] The at least one non-aroma chemical carrier may be a compound, a mixture of compounds, or other additives that have no sensory properties or no noticeable sensory properties. The non-aroma chemical carrier may serve to dilute and / or fix the compound (I) defined above and optionally the at least one aroma chemical, or any other ingredient, if included in the composition.

[0349] A further embodiment of the present invention is directed to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of different compounds (I), and at least one non-fragrance chemical carrier selected from the group consisting of solvents, surfactants, and oil components.

[0350] According to a preferred embodiment of the present invention, said non-fragrance chemical carrier(s) is selected from the solvents, surfactants and oil components listed below.

[0351] One embodiment of the present invention is directed to a composition comprising a compound of formula (I) as described herein, a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of different compounds (I), and at least one solvent.

[0352] In the context of the present invention, a "solvent" is one that does not have a fragrance of its own and serves to dilute the compound(s) (I) used according to the invention and / or any further components of the composition.

[0353] The one or more solvent(s) may be present in the composition in an amount of 0.01-99% by weight relative to the composition. In a preferred embodiment of the present invention, the composition comprises 0.1-90% by weight, preferably 0.5-80% by weight, of the solvent(s) relative to the total weight of the composition. The amount of the solvent(s) can be selected depending on the composition. In one embodiment of the present invention, the composition comprises 0.05-10% by weight, preferably 0.1-5% by weight, more preferably 0.2-3% by weight, relative to the total weight of the composition. In one embodiment of the present invention, the composition comprises 20-70% by weight, preferably 25-50% by weight, of the solvent(s) relative to the total weight of the composition.

[0354] Preferred solvents are ethanol, isopropanol, dipropylene glycol (DPG), propylene glycol, 1,2-butylene glycol, glycerol, diethylene glycol monoethyl ether, diethyl phthalate (DEP), isopropyl myristate (IPM), triethyl citrate (TEC), and benzyl benzoate (BB).

[0355] Particularly preferred solvents are selected from the group consisting of ethanol, propylene glycol, dipropylene glycol, triethyl citrate, benzyl benzoate and isopropyl myristate.

[0356] In a preferred embodiment of the invention, the solvent 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.

[0357] According to a further aspect, the compound of formula (I), its stereoisomers, mixtures of its stereoisomers, mixtures of different compounds (I), or mixtures of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) are used in surfactant-containing compositions according to the invention. Due to their characteristic fragrance properties and their substantivity, retention and stability, the compound of formula (I), its stereoisomers, mixtures of its stereoisomers, mixtures of different compounds (I), or mixtures of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) can be used, inter alia, to provide an odor, preferably a fragrance, impression to surfactant-containing compositions, such as, for example, cleaning agents (in particular laundry care products and all-purpose cleaning agents). It can preferably be used to impart a long-lasting clean note to the surfactant-containing composition.

[0358] Thus, one embodiment of the present invention is directed to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one surfactant.

[0359] The surfactant(s) may be selected from anionic, nonionic, cationic, and / or amphoteric or zwitterionic surfactants. Surfactant-containing compositions, such as shower gels, foam baths, shampoos, etc., preferably contain at least one anionic surfactant.

[0360] The composition according to the invention usually contains the surfactant(s) in an amount of 0-40% by weight, preferably 0-20% by weight, more preferably 0.1-15% by weight, in particular 0.1-10% by weight, based on the total weight of the composition as a whole. Typical examples of non-ionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, optionally partially oxidized alkyl(enyl) oligoglycosides or glucuronic acid derivatives, fatty acid-N-alkylglucamides, protein hydrolysates (in particular wheat-based plant products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. When the non-ionic surfactant contains a polyglycol ether chain, it may have a conventional homolog distribution, but preferably has a narrow range homolog distribution.

[0361] Zwitterionic surfactants contain at least one quaternary ammonium group and at least one -COO (-) group or -SO3 (-) The surface-active compounds containing the group. Particularly suitable zwitterionic surfactants are the so-called betaines, for example N-alkyl-N,N-dimethylammonium glycinates (e.g. cocoalkyldimethylammonium glycinate), N-acylaminopropyl-N,N-dimethylammonium glycinates (e.g. cocoacylaminopropyldimethylammonium glycinate), and 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18 carbon atoms in the alkyl or acyl group, as well as cocoacylaminoethyl hydroxyethyl carboxymethyl glycinate. Particularly preferred are the fatty acid amide derivatives known under the CTFA name of cocamidopropyl betaine.

[0362] Amphoteric surfactants are also particularly suitable as co-surfactants. Amphoteric surfactants are C8-C 18In addition to the alkyl or acyl group, it is a surface-active compound that contains at least one free amino group and at least one -COOH- or -SO3H- group in the molecule and can form an inner salt. Examples of suitable amphoteric surfactants are N-alkyl glycines, N-alkyl propionic acids, N-alkyl amino butyric acids, N-alkyl imino dipropionic acids, N-hydroxyethyl-N-alkyl amidopropyl glycines, N-alkyl taurines, N-alkyl sarcosines, 2-alkyl amino propionic acids, and alkyl amino acetic acids, which contain about 8 to 18 carbon atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-coco alkyl amino propionates, coco acyl amino ethyl amino propionates, and acyl sarcosines.

[0363] Anionic surfactants are characterized by a water-soluble anionic group, such as a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic group. A large number of dermatologically safe anionic surfactants are known to practitioners from relevant textbooks and are commercially available. These are in particular alkyl sulfates in the form of their alkali metal, ammonium or alkanolammonium salts, linear C 1 -C 2 -H 2 -H 3 -H 4 -H 5 -H 6 -H 7 -H 8 -H 9 -H 10 -H 11 -H 12 -H 13 -H 14 -H 15 -H 16 -H 17 -H 18 -H 19 -H 20 -H 21 -H 22 -H 23 -H 24 -H 25 -H 26 -H 27 -H 28 -H 29 -H 30 -H 31 -H 32 -H 33 -H 34 -H 35 -H 36 -H 37 -H 38 -H 39 -H 40 -H 41 -H 42 -H 43 -H 44 -H 45 -H 46 -H 47 -H 48 -H 49 -H 50 -H 51 -H 52 -H 53 -H 54 -H 55 -H 56 -H 57 -H 58 -H 59 -H 60 -H 61 -H 62 -H 63 -H 64 -H 65 -H 66 -H 67 -H 68 -H 69 -H 70 -H 71 -H 72 -H 73 -H 74 -H 75 -H 76 -H 77 -H 78 -H 79 -H 80 -H 81 -H 82 -H 84 -H 85 -H 8 12 These are alkyl ether sulfates, alkyl ether carboxylates, acyl isethionates, acyl sarcosinates, acyltaurines, and sulfosuccinates and acyl glutamates, which contain -8 alkyl or acyl groups.

[0364] Particularly suitable cationic surfactants are quaternary ammonium compounds, preferably ammonium halides, more particularly chlorides and bromides, such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, and trialkylmethylammonium chloride, such as cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, and tricetylmethylammonium chloride.Furthermore, easily biodegradable quaternary ester compounds may be used as cationic surfactants, such as dialkylammonium methosulfate and methylhydroxyalkyldialkoyloxyalkylammonium methosulfate sold under the name Stepantexe, and the corresponding products of the Dehyquart® series."Esterquat" is generally understood to be a quaternized fatty acid triethanolamine ester salt.Esterquat can provide a certain flexibility to the composition. Ester quats are known materials which are prepared by related organic chemistry methods. Other cationic surfactants suitable for use with the present invention are the quaternized protein hydrolysates.

[0365] One embodiment of the present invention is directed to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof or a mixture of different compounds (I) and at least one oil component.

[0366] The oil component is typically present in an amount of from 0.1 to 80% by weight, preferably from 0.5 to 70% by weight, more preferably from 1 to 60% by weight, even more preferably from 1 to 50% by weight, particularly from 1 to 40% by weight, more particularly from 5 to 25% by weight, and especially from 5 to 15% by weight, relative to the total weight of the composition.

[0367] The oil component is, for example, Guerbet alcohols, which are based on fatty alcohols containing 6 to 18, preferably 8 to 10, carbon atoms, as well as other further esters, such as, for example, 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. C may be selected from ester, 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. 18 -C 38 Alkyl hydroxy carboxylic acids and linear or branched C6-C 22 Esters with fatty alcohols (more especially dioctyl malate), esters of linear and / or branched fatty acids with polyhydric alcohols (e.g. propylene glycol, dimer diol or trimer triol), C6-C 10 Triglycerides based on fatty acids, C6-C 18 A mixture of liquid mono-, di- and triglycerides based on fatty acids, C6-C 22Esters of 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-C 22 Fatty alcohol carbonates, such as Guerbet carbonates based on fatty alcohols containing 6 to 18, preferably 8 to 10, carbon atoms, such as dicaprylyl carbonate (Cetiol® CC), benzoic acid and linear and / or branched C6-C 22 Also suitable are esters with alcohols (e.g. Finsolv® TN), linear or branched, symmetrical or asymmetrical dialkyl ethers containing 6 to 22 carbon atoms per alkyl group (e.g. dicaprylyl ether (Cetiol® OE)), ring-opening products of epoxidized fatty acid esters with polyols, and hydrocarbons, or mixtures thereof.

[0368] Antioxidants One embodiment of the present invention is directed to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one antioxidant.

[0369] Antioxidants are capable of inhibiting or preventing undesirable changes in the composition to be protected caused by oxygen effects and other oxidative processes. The effect of antioxidants is in most cases that they act as free radical scavengers against the free radicals generated during autoxidation.

[0370] The antioxidant may, for example, be selected from the group consisting of: - amino acids (e.g. glycine, alanine, arginine, serine, threonine, histidine, tyrosine, tryptophan) and their derivatives, - imidazoles (e.g. urocanic acid) and their derivatives, - peptides, such as D,L-carnosine, D-carnosine, L-carnosine (=β-alanyl-L-histidine) and its derivatives, carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene, lutein) or derivatives thereof, - chlorogenic acid and its derivatives, Lipoic acid and its derivatives (e.g. dihydrolipoic acid), auro-thioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, gamma-linoleyl, cholesteryl and glyceryl esters) and their salts, - Dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts), - sulfoximine compounds (e.g. buthionine sulfoximine, homocysteine ​​sulfoximine, buthionine sulfone, penta-, hexa-, heptathionine sulfoximine) - (metal) chelating agents (e.g. alpha-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), - alpha-hydroxy acids (e.g. citric acid, lactic acid, malic acid), - Humic acid, bile acids, bile extract, bilirubin, biliverdin, boldine (= alkaloids derived from the plant Peumus boldus, boldo extract), - EDTA, EGTA and their derivatives, - unsaturated fatty acids and their derivatives (e.g. gamma-linolenic acid, linoleic acid, oleic acid), - folic acid and its derivatives, - ubiquinone and ubiquinol and their derivatives, - Vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), - tocopherol and derivatives (e.g. vitamin E acetate), - Vitamin A and derivatives (e.g. Vitamin A palmitate), - Coniferyl benzoate of gum benzoin, rutinic acid and its derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol, - Butyl hydroxytoluene (BHT), Butyl hydroxyanisole (BHA), - nordihydroguaiacic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, - Superoxide dismutase - zinc and its derivatives (e.g. ZnO, ZnSO4), - selenium and its derivatives (e.g. selenomethionine), - stilbenes and their derivatives (eg stilbene oxide, trans-stilbene oxide).

[0371] In a preferred embodiment, the antioxidant is selected from the group consisting of pentaerythrityl, tetra-di-t-butyl hydroxyhydrocinnamate, nordihydroguaiaretic acid, ferulic acid, resveratrol, propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), ascorbyl palmitate, and tocopherol.

[0372] The composition according to the present invention may contain an antioxidant in an amount of 0.001 to 25% by weight, preferably 0.005 to 10% by weight, preferably 0.01 to 8% by weight, preferably 0.025 to 7% by weight, preferably 0.05 to 5% by weight, relative to the total weight of the composition.

[0373] Deodorizing agent One embodiment of the present invention is directed to a composition comprising a compound of formula (I), a stereoisomer thereof, a mixture of stereoisomers thereof, a mixture of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one deodorising active.

[0374] Compounds (I), their stereoisomers, mixtures of their stereoisomers, mixtures of different compounds (I), and mixtures of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) can be used to impart a clean, long-lasting note to deodorant compositions and to skin treated with such compositions.

[0375] Deodorant compositions (deodorants and antiperspirants) suppress, mask or eliminate body odor, which is formed through the action of skin bacteria on apocrine sweat, which results in the formation of unpleasant-smelling decomposition products.

[0376] In a preferred embodiment of the present invention, the at least one deodorant active is selected from the group consisting of antiperspirants, esterase inhibitors and antimicrobial agents.

[0377] Suitable antiperspirants can be selected from the group consisting of aluminum, zirconium or zinc salts.Examples are aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and its complex compounds, for example with 1,2-propylene glycol, aluminum hydroxyalantoinate, aluminum tartrate chloride, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and its complex compounds, for example with amino acids such as glycine.Aluminum chlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and their complex compounds are preferably used.

[0378] In a preferred embodiment of the invention, the composition comprises at least one antiperspirant selected from the group consisting of aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate, aluminum hydroxyalantoinate, aluminum tartrate chloride, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate and aluminum zirconium pentachlorohydrate.

[0379] The composition according to the invention may contain the antiperspirant in an amount ranging from 1 to 50% by weight, preferably from 5 to 30% by weight and more particularly from 10 to 25% by weight, relative to the solids content of the composition.

[0380] When sweat is present in the underarm area, extracellular enzymes esterases, mainly proteases and / or lipases, are formed by bacteria and split the esters present in sweat, releasing odor in the process.Suitable esterase inhibitors are, for example, trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate, and especially triethyl citrate.Esterase inhibitors inhibit enzyme activity, thus reducing odor formation.Free acid is released, possibly by cleavage of citrate esters, lowering the pH value of skin to such an extent that enzymes are inactivated by acylation. Other esterase inhibitors are sterol sulfates or phosphates, such as lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfates or phosphates, dicarboxylic acids and their esters, such as 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 their esters, such as citric acid, malic acid, tartaric acid or tartaric acid diethyl ester and zinc glycinate.

[0381] In a preferred embodiment of the invention, the composition comprises at least one esterase inhibitor selected from the group consisting of trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate, triethyl citrate, lanosterol, cholesterol, campesterol, stigmasterol, sitosterol sulfate or 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.

[0382] The composition according to the invention may contain the esterase inhibitor in an amount of 0.01 to 20% by weight, preferably 0.1 to 10% by weight, more particularly 0.5 to 5% by weight, based on the solid content of the composition.

[0383] The term "antibacterial agent" as used herein includes substances that have bactericidal and / or bacteriostatic properties. Typically, these substances act against gram-positive bacteria and include, for example, 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)-urea, 2,4,4'-trichloro-2'-hydroxydiphenyl ether (triclosan), 4-chloro-3,5-dimethylphenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 3-methyl-4-(1-methylethyl)-phenol, 2-benzyl-4-chloro ... ethanol, 3-(4-chlorophenoxy)-propane-1,2-diol, 3-iodo-2-propynyl butylcarbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), phenoxyethanol, glycerol monocaprate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylic acid-N-alkylamides such as salicylic acid-n-octylamide or salicylic acid-n-decylamide.

[0384] In a preferred embodiment, the antimicrobial agent is chitosan, phenoxyethanol, 5-chloro-2-(2,4-dichlorophenoxy)-phenol, 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)-urea, 2,4,4'-trichloro-2'-hydroxydiphenyl ether (triclosan), 4-chloro-3,5-dimethylphenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 3-methyl-4-(1-methyl-2-phenylpropanediol), ...4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)-urea, 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)-urea, 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)-urea, 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)-urea, 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'-( 1,2-Dimethyl-2,4-diphenylphosphine (DMP), 2-(4-methylethyl)-phenol, 2-benzyl-4-chlorophenol, 3-(4-chlorophenoxy)-propane-1,2-diol, 3-iodo-2-propynyl butylcarbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), phenoxyethanol, glycerol monocaprate, glycerol monocaprylate, glycerol monolaurate (GML), diglycerol monocaprate (DMC), salicylic acid-N-alkylamide.

[0385] The composition according to the present invention may contain the antibacterial agent in an amount of 0.01 to 5% by weight, preferably 0.1 to 2% by weight, based on the solid content of the composition.

[0386] The compositions according to the invention may comprise one or more substances, such as, for example, preservatives, abrasives, anti-acne agents, agents for preventing skin aging, anti-cellulite agents, anti-dandruff agents, anti-inflammatory agents, agents for preventing irritation, agents for relieving irritation, astringents, antiperspirants, disinfectants, antistatic agents, binders, buffers, carrier materials, chelating agents, cell stimulants, care agents, depilatories, emulsifiers, enzymes, essential oils, fibres, film formers, fixatives, foam formers, foam stabilisers, substances for preventing foaming, foam boosters, disinfectants, gelling agents, gel formers, hair care agents, hair shaping agents, hair smoothing agents, moisture donating agents, moisturising substances, moisturising substances, bleaching agents, strengthening agents, stain removers, optical brighteners, impregnating agents, soil repellents, antifriction agents, lubricants, moisturising creams, ointments, opacifiers, plasticisers, coatings, polishing agents, gloss agents, polymers, powders, proteins, refatting agents, The composition may further include a skin care agent, a skin exfoliant, a silicone, a skin soothing agent, a skin cleansing agent, a skin care agent, a skin healing agent, a skin whitening agent, a skin protective agent, a skin softener, a cooling agent, a skin cooling agent, a warming agent, a skin warming agent, a stabilizer, a UV absorber, a UV filter, a fabric softener, a suspending agent, a tanning agent, a thickener, a vitamin, a wax, a fat, a phospholipid, a saturated fatty acid, a mono- or polyunsaturated fatty acid, an alpha-hydroxy acid, a polyhydroxy fatty acid, a liquefying agent, a dye, a stain inhibitor, a pigment, an anticorrosive agent, a polyol, an electrolyte, or a silicone derivative.

[0387] The compounds of formula (I) described herein, their stereoisomers, mixtures of their stereoisomers, mixtures of different compounds (I) or mixtures of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) can be used in a wide range of compositions, preferably in perfuming compositions, more preferably in fragrance compositions. The olfactory and material properties of compounds (I) (e.g. solubility in conventional solvents of such compositions and compatibility with further conventional constituents) highlight that the above combinations are particularly suitable for the described uses and compositions.

[0388] Suitable compositions are, for example, perfume compositions, body care compositions (including cosmetic compositions), oral and dental hygiene products, hygiene articles, cleaning compositions (including dishwashing compositions), fabric detergent compositions, compositions for scent dispensers, foods, dietary supplements, pharmaceutical compositions and crop protection compositions.

[0389] The perfume compositions may be selected from fine fragrances, air fresheners in liquid form, in gel form or in the form applied to a solid carrier, aerosol sprays, scented cleansers, scented candles and scented oils (e.g. lamp oils or massage oils).

[0390] Examples of fine fragrances are perfume extracts, eau de parfum, eau de toilette, eau de cologne, eau de solid, and extrait parfum.

[0391] Body care compositions include cosmetic compositions, including aftershave products, preshave products, splash colognes, solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, oil-in-water, water-in-oil, and water-in-oil-in-water cosmetic emulsions (e.g., skin creams and lotions, face creams and lotions, sunscreen creams and lotions, aftersun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, and the like). hair care products (e.g., hair sprays, hair gels, hair setting lotions, hair conditioners, hair shampoos, permanent and semi-permanent hair coloring agents, etc.), hair shaping compositions (e.g., cold wave and hair smoothing compositions, hair tonics, hair creams and hair lotions, etc.), deodorants and antiperspirants (e.g., underarm sprays, roll-ons, deodorant sticks and deodorant creams, etc.), decorative cosmetic products (e.g., eyeliners, eye shadows, nail polishes, make-up, lipsticks, and mascaras, etc.).

[0392] Oral and dental hygiene products may be selected from toothpastes, dental floss, mouthwashes, breath fresheners, dental foams, dental gels and dental strips.

[0393] The hygiene article may be selected from incense sticks, insecticides, repellents, propellants, rust removers, scented cool wipes, underarm pads, baby diapers, sanitary napkins, toilet paper, cosmetic wipes, pocket tissues, dishwashing agents, and deodorants.

[0394] The cleaning compositions (such as solid surface cleaners) may be selected from perfumed acidic, alkaline and neutral cleaners (such as floor cleaners, window cleaners, dishwashing compositions for hand and machine washing of dishes, bathroom and sanitary cleaners, scouring milks, solid and liquid toilet cleaners, powder and foam carpet cleaners, etc.), 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, mould removers and facade cleaners).

[0395] Fabric detergent compositions may be selected from liquid detergents, powder detergents, laundry pre-treatments (such as bleaches, soaking agents and stain removers), fabric softeners, laundry soaps, laundry tablets.

[0396] Food means any untreated, cooked, or processed edible substance, ice, beverage, or composition that is used or intended for use, in whole or in part, for human consumption, or chewing gum, gummies, jellies, and confectioneries.

[0397] Dietary supplements are products intended for ingestion that contain dietary ingredients intended to add additional nutritional value to food. Dietary ingredients can be one or any combination of the following substances: vitamins, minerals, herbs or other botanical substances, amino acids, dietary substances that people use to supplement their diet by increasing their total food intake, concentrates, metabolites, components, or extracts. Dietary supplements can be found in many forms, such as tablets, capsules, softgels, gelcaps, liquids, or powders.

[0398] Pharmaceutical compositions include compositions 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 human or other animal body.

[0399] Crop protection compositions include compositions intended for the management of plant diseases, weeds, and other pests (both vertebrate and invertebrate) that damage agricultural crops and forests.

[0400] The compositions according to the invention may further comprise one or more substances, such as, for example, preservatives, abrasives, anti-acne agents, agents for preventing ageing of the skin, antibacterial agents, anti-cellulite agents, anti-dandruff agents, anti-inflammatory agents, agents for preventing irritation, agents for soothing irritation, antimicrobial agents, antioxidants, astringents, antiperspirants, disinfectants, antistatic agents, binders, buffers, carrier materials, chelating agents, cell stimulants, cleaning agents, care agents, depilatories, surface active substances, deodorants, antiperspirants, emulsifiers, enzymes, essential oils, fibres, film formers, fixatives, foam formers, foam stabilisers, substances for preventing foaming, foam boosters, disinfectants, gelling agents, gel formers, hair care agents, hair shaping agents, hair smoothing agents, moisture donating agents, humectants, moisturising substances, moisturising substances, bleaching agents, strengthening agents, stain removers, optical brighteners, impregnating agents, soil repellents (soil repellents, antifriction agents, lubricants, moisturizing creams, ointments, opacifiers, plasticizers, coatings, polishes, polishes, polymers, powders, proteins, refatting agents, peeling agents, silicones, skin soothing agents, skin cleansing agents, skin care agents, skin healing agents, skin whitening agents, skin protective agents, skin softeners, cooling agents, skin cooling agents, warming agents, skin warming agents, stabilizers, UV absorbers, UV filters, fabric softeners, suspending agents, tanning agents, thickeners, vitamins, waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, alpha-hydroxy acids, polyhydroxy fatty acids, liquefying agents, dyes, stain inhibitors, pigments, corrosion inhibitors, polyols, electrolytes, or silicone derivatives.

[0401] The compounds (I), their stereoisomers, mixtures of their stereoisomers, mixtures of different compounds (I) or mixtures of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) can be incorporated into the composition by simply mixing them directly with the base composition which is devoid of only this / these compound(s). Alternatively, one or more compounds (I), one or more stereoisomers thereof, mixtures of their stereoisomers, mixtures of different compounds (I) or mixtures of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) can be mixed simultaneously or sequentially with the other components of the composition or mixed with a preformed mixture of some of the other components.

[0402] The compounds (I), their stereoisomers, mixtures of their stereoisomers, mixtures of different compounds (I) or mixtures of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2) may in an initial step be encapsulated in an encapsulating material, such as polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, or may be chemically bound to a substrate adapted to release the compounds (I) or their stereoisomers upon application of an external stimulus such as light, enzymes, etc., and then mixed with the composition.

[0403] The compounds (I) according to the invention, their stereoisomers, mixtures of their stereoisomers, mixtures of different compounds (I) or mixtures of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), as well as compositions containing these compounds, may be in microencapsulated, spray-dried, in the form of inclusion complexes or in the form of extruded products. The above properties can be further optimized with regard to a more targeted release of the scent by so-called "coating" with suitable materials, for which purpose preferably waxy synthetic substances are used, such as, for example, polyvinyl alcohol.

[0404] Microencapsulation can be carried out, for example, by the so-called coacervation method using capsule materials, for example made of polyurethane-like substances or soft gelatin. Spray-dried perfume oils can be produced, for example, by spray-drying emulsions or dispersions comprising a compound of formula (I), its stereoisomers, mixtures of its stereoisomers, mixtures of different compounds (I), or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), or a composition of the invention as described herein, where possible carrier materials are modified starches, proteins, dextrins and vegetable gums. Inclusion complexes can be prepared, for example, by introducing a dispersion of the fragrance composition and a cyclodextrin or a urea derivative into a suitable solvent, for example water. The extrusion product can be prepared by dissolving the compound of formula (I) of the present invention described herein, its stereoisomer, a mixture of its stereoisomers, or a mixture of different compounds (I), or a composition, together with a suitable wax-like substance, optionally in a suitable solvent (e.g. isopropanol), and then extruding and solidifying.

[0405] Generally, the total amount of the compounds of formula (I) or their stereoisomers in the compositions according to the invention is typically adapted to the particular intended use or intended application and can therefore vary within a wide range. Usually, the customary standard commercial amounts for fragrances are used.

[0406] The composition according to the invention may contain the compounds of formula (I) or their stereoisomers in a total amount of 0.001 to 99.9% by weight, preferably 0.01 to 90% by weight, more preferably 0.05 to 80% by weight, in particular 0.1 to 60% by weight, even more in particular 0.1 to 40% by weight, for example 0.1 to 10% by weight or 0.1 to 15% by weight, based on the total weight of the composition.

[0407] In one embodiment of the present invention, the composition comprises the compounds of formula (I) or their stereoisomers in a total amount of 0.001 to 5% by weight, preferably 0.01 to 2% by weight, based on the total weight of the composition.

[0408] The following examples serve to further illustrate the invention. EXAMPLES

[0409] Working Example 1. Preparation Examples Abbreviation: HPA Hydroxypivalic aldehyde DMAP: 4-(dimethylamino)-pyridine EA: Ethyl acetate THF: tetrahydrofuran MTBE: Methyl tert-butyl ether RT: room temperature

[0410] analysis: The purity of the product was determined by gas chromatography area %: GC column: HP5 FD (30m (length), 0.25mm (ID), 0.32 micrometer (film)). Temperature program: 50 °C for 5 min, 50 °C to 250 °C at 6° / min, 250 °C for 6 min. Injector: 250°C; detector: 280°C.

[0411] For all samples (except propionate samples, whose purity was determined by area % by gas chromatography): GC column: DB-1701 (30m (length), 0.32mm (ID), 0.25 micrometer (film)). Temperature program: 70 °C for 5 min, 70 °C to 240 °C at 5° / min, 240 °C for 5 min. Injector: 250°C; detector: 280°C.

[0412] The product is 13 Identification was performed by C NMR.

[0413] Example 1: Synthesis of 2-methyl-2-(4-methylenetetrahydropyran-2-yl)propan-1-ol and its double bond isomers (using toluenesulfonic acid monohydrate as catalyst)

[0414] [ka]

[0415] [Table 1]

[0416] A mixture of isoprenol (1) (119.4 g, 1.386 mol) and a 23.6% solution of HPA (2) in toluene (500 g, 1.150 mol) was stirred at 40 °C. At this temperature, toluenesulfonic acid monohydrate (2.2 g, 0.01155 mol) was added to the reaction mixture. The mixture was stirred at reflux (98-113 °C) for 7 h, during which water was distilled during the reaction (23.3 g). After this time, the reaction mixture was set to room temperature and stirred for 17 h. Then, 150 mL of water was added to the mixture and the organic phase was washed twice with a 5% solution of NaHCO3 and with water. The organic extracts were combined, dried over sodium sulfate and the solvent was removed under reduced pressure. The crude product was subjected to distillation separation to obtain the main fraction, which turned out to be a mixture of three elimination products I'-1, I'-2 and I'-3 with a purity of 94% (GC area %). NMR analysis revealed 40% isomer I'-1, 25% isomer I'-2, and 35% isomer I'-3.

[0417] [ka]

[0418] I'-1 isomer:

[0419] [ka]

[0420] I'-1 isomer: 13 C NMR (125 MHz, CDCl3):δ=19.12 (C9), 22.28 (C10), 35.11 (C1), 35.40 (C3), 38.09 (C8), 69.15 (C6), 71.92 (C11), 86.72 (C4), 108.96 (C7), 144.38 (C2).

[0421] I'-2 isomer:

[0422] [ka]

[0423] I'-2 isomer: 13 C NMR (125 MHz, CDCl3):δ= 18.81 (C9), 21.87(C10), 23.04 (C7), 30.07 (C1), 37.66 (C8), 66.26 (C4), 71.60 (C11), 81.13 (C6), 119.08 (C3), 131.73(C2).

[0424] I'-3 isomer:

[0425] [ka]

[0426] I'-3 isomer: 13 C NMR (125 MHz, CDCl3): δ= 19.42, 22.16, 23.47, 30.03, 64.44, 82.22, 120.23, 134.11.

[0427] Example 2: Synthesis of 2-methyl-2-(4-methylenetetrahydropyran-2-yl)propan-1-ol and its double bond isomers (using methanesulfonic acid as catalyst)

[0428] [ka]

[0429] [Table 2]

[0430] A mixture of isoprenol (1) (25.41 g, 0.295 mol) and a 16.8% solution of HPA (2) in toluene (150 g, 0.246 mol) was stirred at 20° C. At this temperature, 2 drops of pure methanesulfonic acid were added to the reaction mixture. The mixture was stirred at reflux (113° C.) for 5 hours, during which water was distilled during the reaction. After this time, 5 drops of methanesulfonic acid were added and the reaction was stirred at reflux for 4 hours. After 9 hours, about 5 mL of water was distilled. The reaction mixture was then set at room temperature. 150 mL of water was added to the mixture and the organic phase was washed with a 5% solution of NaHCO3 and washed with water. The organic extracts were combined and dried over sodium sulfate. The solvent was removed under reduced pressure. The crude product was subjected to distillation separation to obtain the main fraction, which was found to be a mixture of three elimination products I'-1, I'-2 and I'-3 with a purity of 92% (GC area %). NMR analysis revealed 70% isomer I'-1 and 15% each of isomers I'-2 and I'-3.

[0431] [ka]

[0432] Example 3: Synthesis of 2-methyl-2-(4-methylenetetrahydropyran-2-yl)propan-1-ol and its double bond isomers (using methanesulfonic acid as catalyst)

[0433] [ka]

[0434] [Table 3]

[0435] A mixture of isoprenol (1) (72.60 g, 0.853 mol) and a 23.6% solution of HPA (2) in toluene (750 g, 0.71 mol) was stirred at 40° C. At this temperature, 10 drops of methanesulfonic acid were added to the reaction mixture. The mixture was stirred at reflux (113° C.) for 4 hours, during which time water was distilled during the reaction. After this time, 10 drops of methanesulfonic acid were added and the reaction was stirred at reflux for 2.5 hours, and then an additional 20 drops of methanesulfonic acid were added. At this point, water began to distill. The reaction was left at this temperature for an additional 9 hours. After this time, the reaction mixture was set to room temperature. 300 mL of water was added to the mixture and the organic phase was washed with a 5% solution of NaHCO3 and washed with water. The organic extracts were combined and dried over sodium sulfate. The solvent was removed under reduced pressure. The crude product was subjected to distillative separation and two main fractions were collected.

[0436] One of the fractions (fraction 1) was found by NMR to be a mixture of the two elimination products I'-1 (55%) and I'-3 (20%) and the two acetals II'.1 (15%) and II'.2 (5%). This fraction was used to prepare the propionate in Example 8.

[0437] Similarly, the other fraction (fraction 2) was found by NMR to be a mixture of the three elimination products I'-1 (30%), I'-2 (35%) and I'-3 (15%) and the acetal II'.1 (5%). This fraction was used to prepare the methyl ether in Example 10.

[0438] [ka]

[0439] II'.1-isomer; 13 C NMR (125 MHz, CDCl3): δ= 19.93, 21.68, 22.82, 30.25, 38.95, 69.17, 77.14, 107.57.

[0440] II'.2-Isomer: 13 C NMR (125 MHz, CDCl3): δ= 19.82, 20.39, 21.44, 31.69, 35.89, 38.68, 63.16, 69.49, 71.67, 101.41.

[0441] Example 4: Synthesis of 2-methyl-2-(4-methylenetetrahydropyran-2-yl)propan-1-ol and its double bond isomers (using methanesulfonic acid as catalyst)

[0442] [ka]

[0443] [Table 4]

[0444] A mixture of isoprenol (1) (59.7 g, 0.693 mol) and a 23.6% solution of HPA (2) in toluene (250 g, 0.578 mol) was stirred at 40° C. At this temperature, 13 drops of pure methanesulfonic acid were added to the reaction mixture. The mixture was stirred at reflux (113° C.) for 7 h, during which water was distilled during the reaction (10.8 mL). After this time, the reaction mixture was set to room temperature and stirred for 17 h. 100 mL of water was added to the mixture and the organic phase was washed with a 5% solution of NaHCO3 and washed with water. The organic extracts were combined, dried over sodium sulfate and the solvent was removed under reduced pressure. The crude product was subjected to distillation separation to obtain the main fraction, which was found to be a mixture of three elimination products I'-1, I'-2 and I'-3 with a purity of 91% (GC area %). NMR analysis revealed 54% isomer I'-1, 19% isomer I'-2, and 18% isomer I'-3.

[0445] Example 5: Synthesis of 2-methyl-2-(4-methylenetetrahydropyran-2-yl)propan-1-ol and its double bond isomers (using methanesulfonic acid as catalyst)

[0446] [ka]

[0447] The protocol from Example 4 was repeated. After the reaction, the crude product was subjected to distillation separation to obtain a main fraction, which was found to be a mixture of three elimination products I'-1, I'-2 and I'-3 with a purity of 90% (GC area %). GC analysis revealed 46% isomer I'-1, 27% isomer I'-2 and 17% isomer I'-3.

[0448] Example 6: Synthesis of [2-methyl-2-(4-methylenetetrahydropyran-2-yl)propyl]acetate and its double bond isomers

[0449] [ka]

[0450] [Table 5]

[0451] DMAP (0.19 g, 0.002 mol) was added to a solution of the product of Example 2 (9 g, 0.053 mol) in 50 mL of THF at room temperature. The resulting mixture was refluxed at 53° C. while acetic anhydride (6.5 g, 1.2 eq.) was added slowly at this temperature. After 1 h, complete conversion was observed by GC. The reaction was cooled to room temperature and slowly quenched with 50 mL of water. Then, 50 mL of EA was added. The organic phase was separated and washed with saturated aqueous NaHCO3 and then with brine. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 9.6 g of crude product was obtained, which contained about 90% of the title compound by GC analysis (area %). Purification by distillation gave the title compound with a purity of 92% (GC area %). NMR analysis revealed 70% isomer I''-1, 15% each of isomers I''-2 and I''-3.

[0452] [ka]

[0453] I''-1 isomer: 13 C NMR (125 MHz, CDCl3):δ= 19.59 (C9), 20.96 (C10), 21.23 (C15), 35.01 (C1), 35.24 (C3), 37.54 (C8), 69.01 (C6), 70.26 (C11), 82.38 (C4), 108.61 (C7), 145.14 (C2), 171.18 (C13).

[0454] [ka]

[0455] I''-2 isomer: 13C NMR (125 MHz, CDCl3):δ= 19.34 (C12), 20.90 (C11), 20.97 (C10), 23.19 (C6), 29.87 (C2), 37.26 (C7), 66.53 (C5), 70.31 (C8), 77.22 (C1), 119.87 (C4), 132.01(C3), 171.20 (C9).

[0456] [ka]

[0457] I''-3 isomer: 13 C NMR (125 MHz, CDCl3):δ= 19.98 (C12), 20.99 (C11), 21.33 (C10), 23.55 (C6), 30.07 (C4), 38.06 (C7), 64.20 (C5), 70.13 (C8), 78.13 (C1), 119.83 (C2), 134.31(C3), 171.25 (C9).

[0458] Example 7: Synthesis of [2-methyl-2-(4-methylenetetrahydropyran-2-yl)propyl]acetate and its double bond isomers

[0459] [ka]

[0460] [Table 6]

[0461] A sample was prepared according to the protocol described in Example 5. Purification by distillation afforded the title compound with a purity of >95% (GC area %). GC analysis revealed 44% isomer I''-1, 18% isomer I''-2, and 33% isomer I''-3.

[0462] Example 8: Synthesis of [2-methyl-2-(4-methylenetetrahydropyran-2-yl)propyl]propanoate, its double bond isomers and corresponding acetals

[0463] [ka]

[0464] [Table 7]

[0465] DMAP (0.32 g, 0.003 mol) was added to a solution of compounds I'-1, I'-3, II'.1 and II'.2 (15 g, 0.088 mol) obtained in Example 3, fraction 1 in 70 mL of THF at room temperature. The resulting mixture was refluxed at 53°C while propionic anhydride (14.9 g, 1.3 equiv.) was added slowly at this temperature. After 1 h, complete conversion was observed by GC. The reaction was cooled to room temperature and slowly quenched with 50 mL of water. Then, 50 mL of EA was added. The organic phase was separated and washed with saturated aqueous NaHCO3 and then with brine. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 20.9 g of crude product was obtained, which contained about 80% of the title compound according to GC analysis (area %). Purification by distillation gave the title compound with a purity of 96% (GC area %). NMR analysis revealed 50% isomer I''''-1, 20% I''''-3, 20% II''''.1, and 5% II''''.2.

[0466] [ka]

[0467] I'''-1 isomer: 1313C NMR (125 MHz, CDCl3): δ = 9.27 (C14), 19.70 (C15), 21.22 (C16), 27.70 (C13), 35.25 (C1), 35.04 (C3), 37.63 (C8), 69.03 (C6), 70.06 (C9), 82.46 (C4), 108.59 (C7), 145.16 (C2), 174.45 (C11).

[0468]

Chem.

[0469] Isomer I'''-3: 13 13C NMR (125 MHz, CDCl3): δ = 9.27 (C14), 19.70 (C15), 21.22 (C16), 23.54 (C7), 27.70 (C13), 30.08 (C1), 37.63 (C8), 64.20 (C6), 69.38 (C9), 78.18 (C4), 119.89 (C3), 134.26 (C2), 174.38 (C11).

[0470]

Chem.

[0471] II'''.1: 13 13C NMR (125 MHz, CDCl3): δ = 9.24 (C17), 19.46 (C4), 21.32 (C3), 21.71 (C10), 22.85 (C9), 27.67 (C16), 30.19 (C7), 38.46 (C2), 69.38 (C1), 77.21 (C6, C8), 104.36 (C5), 174.48 (C14).

[0472] II'''.2: 13C NMR (126 MHz, CDCl3): δ= 174.45, 97.75, 70.97, 69.55, 63.16, 38.31, 35.88, 31.64, 27.70, 21.43, 19.84, 19.10, 9.27.

[0473] Example 9: Synthesis of [2-methyl-2-(4-methylenetetrahydropyran-2-yl)propyl]propanoate and its double bond isomers

[0474] [ka]

[0475] [Table 8]

[0476] A sample was prepared according to the protocol described in Example 7. Purification by distillation afforded the title compound with a purity of >94% (GC area %). GC analysis revealed 52% isomer I'''-1, 23% isomer I'''-2, and 19% isomer I'''-3.

[0477] [ka]

[0478] Isomer I'''-2: 13 C NMR (126 MHz, CDCl3) δ= 174.51, 132.06, 119.91, 77.29, 70.12, 66.56, 37.35, 29.91, 27.71, 23.20, 20.92, 19.40, 9.27.

[0479] Example 10: Synthesis of 2-(2-methoxy-1,1-dimethyl-ethyl)-4-methylene-tetrahydropyran and its double bond isomers

[0480] [ka]

[0481] [Table 9]

[0482] To a dispersion of sodium hydride (1.3 eq.) in 75 mL of THF, a solution of 8 g of compounds I'-1, I'-2 and I'-3 obtained in Example 3, fraction 2 in 30 mL of THF was slowly added at 0° C. The mixture was stirred at 0° C. for 30 minutes. Then, 1.3 eq. of methyl iodide was slowly added at room temperature. After the addition, the mixture was stirred at 40° C. for 4 hours. The reaction mixture was cooled to 0° C. and the addition of 0.25 eq. of NaH followed by 0.25 eq. of methyl iodide was repeated. Then, the mixture was stirred at 40° C. for 18 hours. The reaction was slowly quenched with 50 mL of water. The organic phase was extracted three times with 50 mL of MTBE. The combined organic extracts were washed with 50 mL of NH3 solution and 50 mL of brine. The combined organic extracts were dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 8.4 g of crude product was obtained, which contained 91% of the desired methyl ether by GC (area %). The crude product was subjected to distillation separation to obtain a major fraction, which was found to be the title compound with a purity of 95% (GC area %). NMR analysis showed 35% isomer I iv -1, 45% I iv -2 and 20% I iv It showed -3.

[0483] [ka]

[0484] I iv -1 isomer: 13C NMR (125 MHz, CDCl3):δ= 20.13 (C13), 20.88 (C12), 35.12 (C1), 35.38 (C3), 37.94 (C8), 59.30 (C11), 69.00 (C6), 79.54 (C9), 82.71 (C4), 108.34 (C7), 145.47 (C2).

[0485] [ka]

[0486] I iv -2 isomer: 13 C NMR (125 MHz, CDCl3):δ= 19.69 (C13), 20.22 (C12), 23.53 (C7), 30.18 (C3), 38.29 (C8), 59.37 (C11), 66.57 (C6), 78.32 (C4), 79.56 (C9), 119.79 (C1), 132.33 (C2).

[0487] I iv -3 isomer: 13 C NMR (125 MHz, CDCl3): δ= 20.22, 21.32, 23.53, 30.18, 38.78, 59.38, 64.37, 78.33, 79.55, 120.55, 133.71.

[0488] Example 11: Synthesis of 2-(2-ethoxy-1,1-dimethyl-ethyl)-4-methylene-tetrahydropyran and its double bond isomer(s):

[0489] [ka]

[0490] [Table 10]

[0491] To a dispersion of sodium hydride (1.3 eq.) in 75 mL of THF, a solution of 10 g of compounds I'-1, I'-2 and I'-3 (46:27:17) obtained in Example 5 in 30 mL of THF was slowly added at 0° C. The mixture was stirred at 0° C. for 30 minutes. Then, 1.3 eq. of ethyl iodide was slowly added at room temperature. After the addition, the mixture was stirred at 50° C. for 4 hours. The reaction mixture was cooled to 0° C. and the addition of 0.25 eq. of NaH followed by 0.25 eq. of ethyl iodide was repeated. Then, the mixture was stirred at 50° C. for 18 hours. The reaction mixture was cooled to 0° C. and the addition of 0.25 eq. of NaH followed by 0.25 eq. of ethyl iodide was repeated again. Then, the mixture was stirred at 50° C. for 6 hours. The reaction was slowly quenched with 50 mL of water. The organic phase was extracted three times with 50 mL of MTBE. The combined organic extracts were washed with 50 mL of NH3 solution and 50 mL of brine. The combined organic extracts were dried over sodium sulfate. After evaporating the solvent under reduced pressure, 10.1 g of crude product was obtained, which contained 91% of the desired ethyl ether by GC (area %). The crude product was subjected to distillation separation to obtain a major fraction, which was found to be the title compound with a purity of 94% (GC area %). NMR analysis showed 50% isomer I v -1, 30% I v -2 and 20% I v It showed -3.

[0492] [ka]

[0493] I v -1 isomer: 13 C NMR (125 MHz, CDCl3): δ= 15.1, 20.24, 21.32, 35.14, 35.41, 38.28, 66.71, 68.99, 76.99, 82.70, 108.25, 145.66.

[0494] I v -2 isomer: 13C NMR (125 MHz, CDCl3): δ= 15.1, 20.03, 21.00, 23.25, 29.99, 37.94, 66.56, 66.73, 76.99, 77.49, 119.81, 132.45.

[0495] I v -3 isomer: 13 C NMR (125 MHz, CDCl3): δ= 15.1, 20.33, 21.32, 23.54, 30.20, 38.82, 64.27, 66.79, 76.99, 78.41, 120.73, 133.50.

[0496] Example 12: Synthesis of (2,2-dimethyl-3-oxo-propyl)acetate

[0497] [ka]

[0498] [Table 11]

[0499] p-Toluenesulfonic acid monohydrate (10.94 g, 0.057 mol) was added to a solution of hydroxypivalinaldehyde (225 g, 1,917 mol) and acetic acid (900 mL, 15.736 mol) in 663 mL of cyclohexane at room temperature. The resulting mixture was refluxed at 72-75 °C and water was removed by Dean-Stark apparatus for 5 h. After water removal, distillation was carried out until the internal temperature reached 133 °C. The crude residue was subjected to fractional distillation to prepare a sample of (2,2-dimethyl-3-oxo-propyl)acetate with a purity of >99 GC area % as a colorless liquid for olfactory testing.

[0500] NMR analysis: 13C NMR (126 MHz, CDCl3) δ= 203.64, 170.95 - 170.93, 67.92, 46.26, 20.70, 18.84, 18.84. H NMR (500 MHz, chloroform-d) δ = 9.53 (s, 1H), 4.12 (s, 2H), 2.05 (s, 3H), 1.12 (s, 6H).

[0501] Example 13: Synthesis of [2-methyl-2-(4-methylenetetrahydropyran-2-yl)propyl]acetate and its double bond isomer

[0502] [ka]

[0503] [Table 12]

[0504] BF3-etherate (2.953 g, 0.0208 mol) was added at room temperature to a solution of HPA-acetate (15 g, 0.099 mol) obtained in Example 12 and 3-methyl-3-buten-1-ol (10.75 g, 0.125 mol) in 165 mL of toluene. The resulting mixture was stirred at 70° C. After 7 h, the reaction mixture was brought to room temperature and washed with 100 mL of saturated aqueous NaHCO3 solution. The phases were separated and the organic phase was dried over sodium sulfate. After filtration and evaporation of the solvent at 60° C. and 150-15 mbar, the crude product was purified by distillation to obtain the title compound with a purity of 97.8% (GC area %) for olfactory testing.

[0505] NMR / GC analysis revealed isomer I''-1 with 2% GC area, isomer I''-2 with 66% GC area, and isomer I''-3 with 30% GC area.

[0506] Example 14: Synthesis of (2,2-dimethyl-3-oxo-propyl)propionate

[0507] [ka]

[0508] [Table 13]

[0509] p-Toluenesulfonic acid monohydrate (10.94 g, 0.057 mol) was added to a solution of hydroxypivalinaldehyde (225 g, 1,917 mol) and propionic acid (904 mL, 12.075 mol) in 662 mL of cyclohexane at room temperature. The resulting mixture was refluxed at 72-76 °C and water was removed by Dean-Stark apparatus for 5 h. After water removal, distillation was carried out until the internal temperature reached 140 °C. The crude residue was subjected to fractional distillation to prepare a sample of (2,2-dimethyl-3-oxo-propyl)propionate with a purity of >99 GC area % as a colorless liquid for olfactory testing.

[0510] NMR analysis: 13 C NMR (126 MHz, CDCl3) δ= 203.60, 174.15, 67.77, 46.37, 27.36, 18.82, 18.82, 9.05. 1 H NMR (500 MHz, chloroform-d) δ = 9.54 (s, 1H), 4.13 (s, 2H), 2.33 (d, J = 7.7 Hz, 2H), 1.12 (s, 9H).

[0511] Example 15: Synthesis of [2-methyl-2-(4-methylenetetrahydropyran-2-yl)propyl] propanoate and its double bond isomers

[0512] [ka]

[0513] [Table 14]

[0514] BF3-etherate (4.3 g, 0.003 mol) was added to a solution of HPA-propionate (24 g, 0.147 mol) and 3-methyl-3-buten-1-ol (15.68 g, 0.182 mol) in 241 mL of toluene at room temperature. The resulting mixture was stirred at 90 °C. After 4 h, the reaction mixture was brought to room temperature and washed with 50 mL of saturated aqueous NaHCO3 solution. The phases were separated and the organic phase was dried over sodium sulfate. After filtration and evaporation of the solvent at 60 °C and 150-10 mbar, the crude product was purified by distillation to give the title compound with a purity of 98% (GC area %) for olfactory testing.

[0515] GC analysis revealed isomer I'''-1 with 2% GC area, isomer I'''-2 with 62% GC area, and isomer I'''-3 with 35% GC area.

[0516] [ka]

[0517] Isomer I'''-2: 13 C NMR (126 MHz, CDCl3) δ= 174.51, 132.06, 119.91, 77.29, 70.12, 66.56, 37.35, 29.91, 27.71, 23.20, 20.92, 19.40, 9.27. 1 H NMR (500 MHz, chloroform-d) δ = 5.45 - 5.37 (m,1H), 4.22 - 3.88 (m, 4H), 3.33 (dd, J = 11.1, 3.1 Hz, 1H), 2.45 - 2.02 (m, 3H), 1.78 - 1.60 (m,4H), 1.20-1.11 (m,3H), 0.99 - 0.90 (s 6H).

[0518] Isomer I'''-3: 13C NMR (126 MHz, CDCl3) δ= 174.51, 134.30, 119.91, 78.20, 69.94, 64.22, 38.18, 30.08, 27.71, 23.55, 21.33, 20.05, 9.24. 1 H NMR (500 MHz, chloroform-d) δ = 5.45 - 5.35z (m, 1H), 4.10 - 3.88 (m, 3H), 3.86 (s, 1H), 3.53 (td, J = 11.2, 3.4 Hz, 1H), 2.41 - 2.16 (m, 3H), 1.78 - 1.59 (m, 4H), 1.20-1.11 (m, 3H), 0.93 - 0.86 (s,6H).

[0519] 2. Olfactory test To test the odour quality and intensity of the compound (I) of the present invention, a scent strip test was carried out.

[0520] For this purpose, strips of absorbent paper were immersed in a solution containing a 1-10% by weight solution of the tested compound (I) in ethanol or triethyl citrate. After evaporation of the solvent (approximately 30 seconds), the scent impression was olfactory evaluated by a trained perfumer.

[0521] The results of the odor tests are summarized in Table 1.

[0522] [Table 15] TIFF0007638995000064.tif223161TIFF0007638995000065.tif202161

[0523] Commercial products and advantageous fragrance compositions

[0524] Solution A is the undiluted product of Example 1. Solution B is the undiluted product of Example 6. Solution C is the undiluted product of Example 7. Solution D is the undiluted product of Example 8. Solution E is the undiluted product of Example 9. Solution F is the undiluted product of Example 10. Solution G is the undiluted product of Example 11. Solution H is the undiluted product of Example 13. Solution I is the undiluted product of Example 15.

[0525] Advantageous fragrance compositions: The above solution A was formulated into a composition according to Table 2. The amounts shown in Table 2 are in units of weight (g).

[0526] [Table 16]

[0527] The above solution A was formulated into a composition according to Table 3. The amounts shown in Table 3 are in units of weight (g).

[0528] [Table 17]

[0529] Fragrance Composition 3 corresponds to Fragrance Composition 1A, where Solution A is replaced with an equal amount of Solution B. Fragrance Composition 4 corresponds to Fragrance Composition 1B, where Solution A is replaced with an equal amount of Solution B. Fragrance Composition 5 corresponds to Fragrance Composition 2A, where Solution A is replaced with an equal amount of Solution B. Fragrance Composition 6 corresponds to Fragrance Composition 2B, where Solution A is replaced with an equal amount of Solution B.

[0530] Fragrance Composition 7 corresponds to Fragrance Composition 1A, where Solution A is replaced with an equal amount of Solution C. Fragrance Composition 8 corresponds to Fragrance Composition 1B, where Solution A is replaced with an equal amount of Solution C. Fragrance Composition 9 corresponds to Fragrance Composition 2A, where Solution A is replaced with an equal amount of Solution C. Fragrance Composition 10 corresponds to Fragrance Composition 2B, where Solution A is replaced with an equal amount of Solution C.

[0531] Fragrance composition 11 corresponds to fragrance composition 1A, where solution A is replaced with an equal amount of solution D. Fragrance composition 12 corresponds to fragrance composition 1B, where solution A is replaced with an equal amount of solution D. Fragrance composition 13 corresponds to fragrance composition 2A, where solution A is replaced with an equal amount of solution D. Fragrance composition 14 corresponds to fragrance composition 2B, where solution A is replaced with an equal amount of solution D.

[0532] Fragrance composition 15 corresponds to fragrance composition 1A, where solution A is replaced with an equal amount of solution E. Fragrance composition 16 corresponds to fragrance composition 1B, where solution A is replaced with an equal amount of solution E. Fragrance composition 17 corresponds to fragrance composition 2A, where solution A is replaced with an equal amount of solution E. Fragrance composition 18 corresponds to fragrance composition 2B, where solution A is replaced with an equal amount of solution E.

[0533] Fragrance composition 19 corresponds to fragrance composition 1A, where solution A is replaced with an equal amount of solution F. Fragrance composition 20 corresponds to fragrance composition 1B, where solution A is replaced with an equal amount of solution F. Fragrance composition 21 corresponds to fragrance composition 2A, where solution A is replaced with an equal amount of solution F. Fragrance composition 22 corresponds to fragrance composition 2B, where solution A is replaced with an equal amount of solution F.

[0534] Fragrance composition 23 corresponds to fragrance composition 1A, where solution A is replaced with an equal amount of solution G. Fragrance composition 24 corresponds to fragrance composition 1B, where solution A is replaced with an equal amount of solution G. Fragrance composition 25 corresponds to fragrance composition 2A, where solution A is replaced with an equal amount of solution G. Fragrance composition 26 corresponds to fragrance composition 2B, where solution A is replaced with an equal amount of solution G.

[0535] Fragrance composition 27 corresponds to fragrance composition 1A, where solution A is replaced with an equal amount of solution H. Fragrance composition 28 corresponds to fragrance composition 1B, where solution A is replaced with an equal amount of solution H. Fragrance composition 29 corresponds to fragrance composition 2A, where solution A is replaced with an equal amount of solution H. Fragrance composition 30 corresponds to fragrance composition 2B, where solution A is replaced with an equal amount of solution H.

[0536] Fragrance composition 31 corresponds to fragrance composition 1A, where solution A is replaced with an equal amount of solution I. Fragrance composition 32 corresponds to fragrance composition 1B, where solution A is replaced with an equal amount of solution I. Fragrance composition 33 corresponds to fragrance composition 2A, where solution A is replaced with an equal amount of solution I. Fragrance composition 34 corresponds to fragrance composition 2B, where solution A is replaced with an equal amount of solution I. The following is one embodiment of the present invention. (1) Formula (I): [ka] (In the formula, R 1 、R 2 、R 3 and R 4 is hydrogen; or R 2 、R3 or R 4 One of them is R 1 Together with R represents a double bond. 2 、R 3 or R 4 all of the remainder are hydrogen; R 5 is hydrogen, C 1 -C 4 -Alkyl and -C(=O)-R 6 wherein R 6 is hydrogen and C 1 -C 4 -alkyl) or a mixture thereof, a stereoisomer thereof, or a mixture of stereoisomers thereof; Alternatively, at least one compound of formula (I) and a compound of formula (II.1) and / or (II.2):

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Claims

1. Formula (I): 【Chemistry 1】 (In the formula, R 1 , R 2 , R 3 and R 4 is hydrogen; or R 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4 all the remainder are hydrogen; R 5 is hydrogen, C 1 -C 4 -Alkyl and -C(=O)-R 6 wherein R 6 is hydrogen and C 1 -C 4 -alkyl) or a mixture thereof, a stereoisomer thereof, or a mixture of stereoisomers thereof; Alternatively, at least one compound of formula (I) and a compound of formula (II.1) and / or (II.2): 【Chemistry 2】 (In the formula, R 5 is as defined above) A mixture of one or both of the compounds.

2. In the compound of formula (I), R 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4 The compound of claim 1 , wherein all of the remainder are hydrogen.

3. A mixture comprising at least two of compounds (I-1), (I-2) and (I-3), wherein compound (I-1) is R 2 R 1 Together with R represents a double bond. 3 and R 4 is hydrogen, and compound (I-2) is a compound of formula (I) in which R 3 R 1 Together with R represents a double bond. 2 and R 4 is hydrogen, and compound (I-3) is a compound of formula (I) in which R 4 R 1 Together with R represents a double bond. 2 and R 3 The compound according to claim 2, which is a compound of formula (I), wherein is hydrogen.

4. The compound according to claim 3, which is a mixture containing compound (I-1), compound (I-3) and optionally compound (I-2).

5. 5. A compound according to any one of claims 1 to 4, which is a mixture comprising at least one of compounds (I-1), (I-2) and / or (I-3) as defined in claim 3, and further comprising one or both of compounds of formulae (II.1) and / or (II.2).

6. R 5 But, C 1 -C 4 6. The compound according to claim 1, wherein:

7. R 5 The compound according to any one of claims 1 to 5, wherein is hydrogen.

8. R 5 -C(=O)-R 6 where R 6 is hydrogen or C 1 -C 4 6. The compound according to claim 1, wherein:

9. A composition comprising a compound of formula (I) as defined in any one of claims 1 to 8, a mixture thereof, a stereoisomer thereof, a mixture of stereoisomers thereof, or a mixture of at least one compound of formula (I) with one or both of the compounds of formula (II.1) and / or (II.2), and at least one further ingredient selected from the group consisting of aroma chemicals different from compounds (I), (II.1) and (II.2), non-aroma chemical carriers, antioxidants and deodorising actives.

10. The composition of claim 9, wherein at least one further component is selected from the group consisting of fragrance chemicals different from compounds (I), (II.1) and (II.2), surfactants, oil components, solvents, antioxidants and deodorant actives.

11. 11. The composition according to claim 9 or 10, selected from the group consisting of perfume compositions, body care compositions, oral or dental hygiene products, hygiene articles, cleaning compositions, fabric detergent compositions, compositions for scent dispensers, food products, dietary supplements, pharmaceutical compositions and crop protection compositions.

12. Use of a compound of formula (I) as defined in any one of claims 1 to 8, a mixture thereof, a stereoisomer thereof, a mixture of stereoisomers thereof or a mixture of at least one compound of formula (I) with one or both of the compounds of formulae (II.1) and / or (II.2) as aroma chemical.

13. Use of a compound of formula (I) as defined in any one of claims 1 to 8, a mixture thereof, a stereoisomer thereof, a mixture of stereoisomers thereof or a mixture of at least one compound of formula (I) with one or both of the compounds of formulae (II.1) and / or (II.2) for modifying and / or enhancing the odor of a composition.

14. 14. Use according to claim 12 or 13 in a composition selected from perfume compositions, body care compositions, oral or dental hygiene products, hygiene articles, cleaning compositions, fabric detergent compositions, compositions for scent dispensers, foods, dietary supplements, pharmaceutical compositions and crop protection compositions.

15. A process for preparing a compound of formula (I) as defined in any one of claims 1 to 8, a mixture thereof, a stereoisomer thereof, a mixture of stereoisomers thereof or a mixture of at least one compound of formula (I) with one or both of the compounds of formulae (II.1) and / or (II.2), comprising the following steps: (a) 3-Methylbut-3-en-1-ol (isoprenol) is reacted with 3-hydroxy-2,2-dimethyl-propanal (hydroxypivalinaldehyde) in an acidic medium to give a compound of formula (I') and, optionally, of formula (II'.1) and / or (II'.2): 【Chemistry 3】 【change】 (In the formula, R 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4 the rest are all hydrogen) obtaining a reaction mixture containing one or both of the compounds of (b) optionally isolating the compound of formula (I') and, if present, compounds (II'-1) and (II'-2) from the reaction mixture obtained in step (a) or enriching it in the reaction mixture obtained in step (a); (c) a compound of formula (I) or a compound of formula (I') 1 , R 2 , R 3 and R 4 is hydrogen), the reaction mixture obtained in step (a) or the product obtained in step (b) is subjected to a hydrogenation reaction to prepare a compound of formula (I'), 1 , R 2 , R 3 and R 4 is hydrogen; (d) R 5 is not hydrogen is prepared: subjecting the reaction mixture obtained in step (a) or the product obtained in step (b) or the product obtained in step (c) to an etherification reaction or an esterification reaction; (e) a compound of formula (I), 1 , R 2 , R 3 and R 4 is hydrogen, and R 5 is not hydrogen) is prepared, and if step (c) has not been carried out: subjecting the product obtained in step (d) to a hydrogenation reaction; and (f) optionally subjecting the product obtained in step (b), or step (c), or step (d), or step (e) to a purification step. The method comprising:

16. A compound of formula (I) as defined in any one of claims 1 to 4, 6 or 8, wherein R 5 is C 1 -C 4 -Alkyl and -C(=O)-R 6 A method for preparing a mixture thereof, a stereoisomer thereof, or a mixture of stereoisomers thereof, comprising the steps of: (i) 3-hydroxy-2,2-dimethyl-propanal (hydroxypivalinaldehyde) is subjected to an etherification reaction or an esterification reaction to obtain a product of formula 3: 【Chemistry 4】 (In the formula, R 5a is C 1 -C 4 -Alkyl and -C(=O)-R 6 (selected from the group consisting of obtaining a reaction mixture comprising a compound of formula (I); (ii) optionally isolating the compound of formula 3 from the reaction mixture obtained in step (i) or enriching it in the reaction mixture obtained in step (i); (iii) The reaction mixture obtained in step (i) or the product obtained in step (ii) and 3-methylbut-3-en-1-ol (isoprenol) are reacted with BF 3 source to give a compound of formula (I), 2 , R 3 or R 4 One of them is R 1 Together with R represents a double bond. 2 , R 3 or R 4 The remainder of are hydrogen, and R 5 is C 1 -C 4 -Alkyl and -C(=O)-R 6 obtaining a reaction mixture comprising: (iv) a compound of formula (I) 1 , R 2 , R 3 and R 4 is hydrogen, and R 5 is C 1 -C 4 -Alkyl and -C(=O)-R 6 (selected from the group consisting of): subjecting the product obtained in step (iii) to a hydrogenation reaction; and (v) optionally subjecting the product obtained in step (iii) or step (iv) to a purification step. The method comprising:

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