2-Furyl- and 2-thienyl-substituted dihydropyrans and tetrahydropyrans as aroma chemicals

Abstract

The present invention relates to the use of 2-furanyl- and 2-thienyl-substituted dihydropyrans and tetrahydropyrans of formula (I) as aromatic chemicals, wherein the variables are defined in the claims and the specification; to an aromatic chemical composition comprising at least one 2-furanyl- or 2-thienyl-substituted dihydropyran or tetrahydropyran, and a method for preparing the aromatic chemical composition. The present invention further relates to specific 2-furanyl- and 2-thienyl-substituted dihydropyrans and tetrahydropyrans and methods for preparing them.

Description

[0001] The present invention relates to the use of 2-furanyl- and 2-thienyl-substituted dihydropyrans and tetrahydropyrans as aroma chemicals, to aroma chemical compositions comprising at least one 2-furanyl- or 2-thienyl-substituted dihydropyran or tetrahydropyran, and to methods for preparing aroma chemical compositions, in particular perfuming compositions, especially perfuming ready-to-use compositions, which comprise incorporating at least one 2-furanyl- or 2-thienyl-substituted dihydropyran or tetrahydropyran into such compositions. The present invention further relates to specific 2-furanyl- and 2-thienyl-substituted dihydropyrans and tetrahydropyrans and methods for their preparation. Background of the Invention

[0003] Aroma chemicals, especially fragrances, are of particular interest in the field of cosmetics and cleaning and laundry compositions. Fragrances of natural origin are mostly expensive, are often in limited supply, and their content, purity, etc., also vary due to fluctuating environmental conditions. In order to circumvent these undesirable factors, it is therefore of great interest to produce synthetic substances that have organoleptic properties similar to those of more expensive natural fragrances or that have novel and interesting organoleptic properties.

[0004] Despite the existence of a large number of synthetic aromachemicals (flavors and fragrances), there is a constant need for new components that can meet the numerous properties required for extremely diverse fields of application. These include, firstly, organoleptic properties, i.e. the compounds should have favorable odor (olfactory) or taste properties. In addition, aromachemicals should at all events also have further positive secondary properties, such as efficient preparation methods, the possibility of providing better sensory attributes due to synergistic effects with other flavors, higher stability under certain application conditions, higher scalability, better lasting power, etc.

[0005] However, the targeted search for substances with specific organoleptic properties, such as a specific odor, is extremely difficult, since even small changes in chemical structure can lead to large changes in organoleptic properties, such as odor and taste. The search for new flavors and fragrances is therefore in most cases difficult and laborious, without knowing whether a substance with the desired odor and / or taste will actually be found.

[0006] 2,4,4-trisubstituted tetrahydropyran compounds have been mentioned many times as aromatic chemicals. For example, EP0383446A2 describes 2,4,4-trisubstituted tetrahydropyrans of formula (A) in which R I is methyl or ethyl and R II is a straight-chain or branched C2-C4-alkyl or C2-C4-alkenyl group.

[0007] US 4,962,090 describes 2,4-disubstituted and 2,2,4-trisubstituted tetrahydropyranyl-4-ethers of the formula (B) in which R' represents methyl or ethyl and R a and R b is selected from hydrogen, phenyl, C1-C8-alkyl and C2-C8-alkenyl or together represent C5-C 12 - Cycloalkyl or alkylcycloalkyl.

[0008]

[0009] L. Liu et al., J. Am. Chem. Soc. 2016, 138, 10822-10825 describe a method for preparing chiral 2-substituted 4-methylenetetrahydropyrans by asymmetric Prins cyclization of aromatic or aliphatic aldehydes with 3-methylprop-3-en-1-ol. In particular, the synthesis of 2-(furan-2-yl)-4-methylenetetrahydropyran and its regioisomers is described.

[0010] JA Marco et al. describe the synthesis of conjugated γ- and δ-lactones from aldehydes and ketones by ring-closing metathesis in Tetrahedron 2003, 59, 4085-4101. In particular, the synthesis of 2-(2-furyl)-4-methyl-3,6-dihydro-2H-pyran is described.

[0011] 2-Furyl- and 2-thienyl-substituted dihydropyrans and tetrahydropyrans have not been proposed as aroma chemicals so far. SUMMARY OF THE INVENTION

[0013] It is an object of the present invention to provide substances which exhibit pleasant organoleptic properties and can be advantageously used as aroma chemicals. Another object of the present invention is to provide substances which can be used as aroma chemicals in ready-to-use compositions. Strong-smelling substances with a pleasant odor are particularly sought. Furthermore, these aroma chemicals should be combinable with other aroma chemicals to create novel advantageous organoleptic properties. Furthermore, these aroma chemicals should be obtainable from readily available raw materials so that they can be manufactured quickly and economically.

[0014] Surprisingly it was found that this is achieved by compounds of formula (I), by mixtures thereof [meaning mixtures of two or more different compounds (I), for example 2, 3 or 4 different compounds (I)], by stereoisomers thereof and by mixtures of stereoisomers thereof.

[0015] Accordingly, the first aspect of the present invention relates to the use of compounds of general formula (I), including their stereoisomers, as aroma chemicals:

[0016]

[0017] in

[0018] X is O or S;

[0019] R 1 is hydrogen, OH, O-C1-C4-alkyl or O-(C=O)-R 5 ;

[0020] R 2 , R 3 , R 4 It is hydrogen;

[0021] or R 2 , R 3 , R 4 One and R 1 together represent a double bond; and

[0022] R 5 is selected from hydrogen and C1-C4-alkyl.

[0023] The present invention also relates to the use of mixtures of different compounds of formula (I), including mixtures of double bond isomers and mixtures of stereoisomers thereof, as aroma chemicals.

[0024] The present invention further relates to an aromachemical composition comprising at least one compound of formula (I) as defined above, its stereoisomers or mixtures of its stereoisomers, and at least one additional compound selected from aromachemicals different from compound (I) and non-aromachemical carriers.

[0025] It has further been found that the compounds of general formula (I) generally exhibit a pleasant and characteristic odor and can be used to produce perfuming ready-to-use compositions. Furthermore, they can advantageously be combined with other aroma chemicals different from compound (I) to create new scent profiles.

[0026] The present invention therefore further relates to a process for preparing an aromachemical composition, in particular a perfuming composition, especially a perfuming ready-to-use composition, which comprises incorporating into the composition, in particular a ready-to-use composition, at least one compound of formula (I), its stereoisomers or a mixture of its stereoisomers.

[0027] The invention also relates to the use of a compound of formula (I), its stereoisomers, mixtures of its stereoisomers or mixtures of different compounds (I) as defined above for modifying the aroma profile of a perfuming ready-to-use composition.

[0028] In the class of compounds of formula (I), 2-(2-furyl)-tetrahydropyran compounds of formula (Ia) below and 2-(2-thienyl)-tetrahydropyran compounds of formula (Ib) below have not been described in the art.

[0029] Therefore, the present invention also relates to novel compounds of the general formula (Ia), mixtures of different compounds (Ia), their stereoisomers or mixtures of their stereoisomers:

[0030]

[0031] in

[0032] R 1 is hydrogen, OH, O-C1-C4-alkyl or O-(C=O)-R 5 ,and

[0033] R 5 is selected from hydrogen and C1-C4-alkyl;

[0034] Also disclosed are methods of producing such compounds.

[0035] Furthermore, the present invention relates to novel compounds of the general formula (Ib), mixtures of different compounds (Ib), their stereoisomers or mixtures of their stereoisomers:

[0036]

[0037] in

[0038] R 1 is hydrogen, OH, O-C1-C4-alkyl or O-(C=O)-R 5 ,

[0039] R 2 , R 3 , R 4 It is hydrogen;

[0040] or R 2 , R 3 , R 4 One and R 1 together they represent a double bond;

[0041] R 5 is selected from hydrogen and C1-C4-alkyl;

[0042] Also disclosed are methods of producing such compounds.

[0043] The present invention also relates to a mixture of at least two different compounds of formula (I). In particular, the mixture comprises two or three double bond isomers of the compounds of formula (I).

[0044] The compounds of formula (I), their mixtures, their stereoisomers or their mixtures of stereoisomers have favorable organoleptic properties, in particular a pleasant odor. Therefore, they can be advantageously used as fragrance chemicals in, for example, perfume compositions, body care compositions (including cosmetic compositions), oral dental hygiene products, hygiene products, cleaning compositions (including dishwashing compositions), fabric detergent compositions, compositions for diffusers, pharmaceutical compositions, crop protection compositions and other ready-to-use compositions.

[0045] By virtue of their physical properties, the compounds of formula (I), their stereoisomers or their mixtures of stereoisomers have particularly good, almost universal solvent properties for other essences and other conventional ingredients in perfuming ready-to-use compositions, such as, in particular, perfume compositions. Therefore, the compounds of formula (I), their stereoisomers or their mixtures of stereoisomers can be advantageously combined with other aroma chemicals, thereby making it possible in particular to create perfume compositions having novel advantageous sensory properties.

[0046] In addition, the compound of formula (I), their stereoisomer or their mixture of stereoisomer can be produced in good yield and purity by single-step or two-step synthesis from readily available raw material compounds. Therefore, the compound of formula (I), their stereoisomer or their mixture of stereoisomer can be produced on a large scale and in a simple and cost-effective manner. DETAILED DESCRIPTION OF THE INVENTION

[0048] In the present invention, the phrase "C1-C4-alkyl" refers to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl. Preferably, the phrase "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.

[0049] If R 2 , R 3 , R 4 One and R 1 together represent a double bond, which of course means that the double bond is present in R 2 , R 3 or R 4 and R 1 The bonds between the carbon atoms bonded to and by R 2 , R 3 or R 4 With R 1 The bond formed together forms. Therefore, if R 2 With R 1 Together they represent a double bond, which yields a compound of formula (I-1).3 With R 1 Together they represent a double bond, which yields a compound of formula (I-2). 4 With R 1 Together they represent a double bond, which yields compounds of formula (I-3).

[0050]

[0051] These compounds can be viewed as double bond isomers of each other.

[0052] Since R in compound I-1 3 and R 4 is H, R in compound I-2 2 and R 4 is H, and R in compound I-3 2 and R 3 is H, the compounds of formula I-1, I-2 and I-3 can be more simply depicted as follows:

[0053]

[0054] If R 1 is H, compound (I) is a compound of formula (I-4). 1 is OH, compound (I) is a compound of formula (I-5). 1 is O-C1-C4-alkyl, and compound (I) is a compound of formula (I-6).

[0055] If R 1 O-(C=O)-R 5 , compound (I) is a compound of formula (I-7).

[0056]

[0057] The term "stereoisomer" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to the presence of more than one stereocenter in a molecule, and geometric isomers (cis / trans isomers) as a specific form of diastereomers. The compounds of formula (I) have at least one stereocenter, i.e. a carbon atom of a dihydropyran or tetrahydropyran ring carrying a furan (X=O) or thiophene ring (X=S). If R 1 is hydrogen, OH, O-C1-C4-alkyl or O-(C=O)-R 5 The compound of formula (I) has one more stereocenter (i.e., in the dihydropyran or tetrahydropyran carrying R 1The invention provides the pure enantiomers or diastereomers and mixtures thereof, and the use according to the invention of the pure enantiomers or diastereomers of compound (I) or mixtures thereof.

[0058] In this document, the term "compound I", "compound (I)" or "compound of formula (I)" refers to the compound form obtained in the non-stereoselective process for its production when no specific stereoisomer or specific stereoisomer mixture is specified. However, this term is also used if it is not necessary or possible to specify the stereochemistry of compound (I) in more detail.

[0059] If a compound of formula (I) is specified hereinafter as a specific, specified compound (and not a mixture of different compounds I), this means that the compound contains less than 5% by weight, preferably less than 3% by weight and particularly preferably less than 1% by weight of other compounds I, relative to the total weight of the specific, specified compound I and any other compounds I present.

[0060] In mixtures containing different compounds (I), these may differ in one or more radicals R 1 To R 4 and / or the definition of X. Preferably, the compounds in the mixture differ only in one or more radicals R 1 To R 4 Definition. More preferably, the mixture contains two or three of compounds (I-1), (I-2) and (I-3). Due to the preparation method, such a mixture may also contain a minor amount of compound (I-5). "Minor amount" refers to less than 3 weight percent, preferably less than 1 weight percent relative to the total weight of compounds (I-1), (I-2), (I-3) and (I-5) contained in the mixture. In general, a mixture of two or three of compounds (I-1), (I-2) and (I-3) is a mixture of double bond isomers, which means that in all compounds (I-1), (I-2) and (I-3) contained in the mixture (and if present, in compound (I-5)), X has the same meaning and is therefore O or S in each case. Mixtures in which X in (I-1), (I-2) and / or (I-3) has different meanings are also suitable for the purpose of the present invention, but are less economical, because mixtures in which X in all compounds (I) has the same meaning are usually automatically formed during the production process.

[0061] In a preferred embodiment of the present invention, in the compounds of general formula (I), X is O.

[0062] In another preferred embodiment of the present invention, in the compounds of general formula (I), X is S.

[0063] In a preferred embodiment of the present invention, in the compounds of general formula (I), R 2 , R 3 , R 4 One and R 1 together represent a double bond.

[0064] More preferably, the compound of formula (I) is compound (I-1), wherein R 2 With R 1 together represent a double bond, or a compound (I-2) in which R 3 With R 1 together represent a double bond, or a compound (I-3) in which R 4 With R 1 Together they represent a double bond, or a mixture of at least two of the compounds (I-1), (I-2) and (I-3). Such a mixture of at least two of the compounds (I-1), (I-2) and (I-3) is preferably a mixture of double bond isomers of the compound (I), meaning that X has the same meaning in all the compounds (I-1), (I-2) and (I-3) contained in the mixture.

[0065] Compound (I-1), compound (I-2), compound (I-3) or a mixture of at least two compounds (I-1), (I-2) and (I-3) may contain a minor amount of 1 Compound I [compound (I-5)] wherein R is OH. "Minor amount" means less than 3% by weight, preferably less than 1% by weight, relative to compounds (I-1), (I-2) and (I-3) or mixtures thereof, including compounds wherein R 1 is based on the total weight of compound I containing OH.

[0066] In a particular embodiment, the compound of formula (I) is compound (I-1), wherein R 2 With R 1 In another specific embodiment, the compound of formula (I) is compound (I-2), wherein R 3 With R 1 In another specific embodiment, the compound of formula (I) is compound (I-3), wherein R 4 With R 1 Together they represent a double bond. Specifically, the compound of formula (I) is compound (I-2).

[0067] In yet another specific embodiment, the compound of formula (I) is a mixture of at least two of compounds (I-1), (I-2) and (I-3). More particularly, the mixture contains compound I-2 and one or both of compounds I-1 and I-3. In an alternative more specific embodiment, the mixture contains compounds I-1 and I-2 and optionally also contains compound I-3. In another alternative more specific embodiment, the mixture contains compounds (I-2) and (I-3); or contains all three compounds (I-1), (I-2) and (I-3).

[0068] In particular, the mixture contains compounds I-2 and I-3 and optionally also contains compound I-1, wherein compound I-1 is contained in an amount of 0 to 10% by weight, compound I-2 is contained in an amount of 1 to 80% by weight, and compound I-3 is contained in an amount of 15 to 99% by weight, relative to the total weight of compounds I-1, I-2 and I-3. Preferably, the mixture is a mixture of double bond isomers, meaning that in compounds (I-2) and (I-3) contained in the mixture, X has the same meaning. Specifically, the mixture contains all three compounds (I-1), (I-2) and (I-3), wherein compound I-1 is contained in an amount of 0.1 to 10% by weight, compound I-2 is contained in an amount of 1 to 79.9% by weight, and compound I-3 is contained in an amount of 15 to 99% by weight, relative to the total weight of compounds I-1, I-2 and I-3. Preferably, the mixture is a mixture of double bond isomers, meaning that in all compounds (I-1), (I-2), (I-3) contained in the mixture, X has the same meaning.

[0069] In a specific embodiment of the binary mixture of compounds (I-2) and (I-3), compound (I-3) is predominant, i.e. it is present in an amount of more than 50% by weight, based on the weight of the mixture consisting of compounds (I-2) and (I-3). In particular, it is present in an amount of 70 to 99% by weight, more particularly 75 to 98% by weight, especially 75 to 95% by weight, based on the weight of the mixture consisting of compounds (I-2) and (I-3); the difference to 100% is compound (I-2).

[0070] In a specific embodiment of the ternary mixture of compounds (I-1), (I-2) and (I-3), compound (I-2) is predominant. In particular, it is present in an amount of 50 to 80% by weight, more particularly 55 to 75% by weight, especially 60 to 70% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). In particular, in the ternary mixture, compound (I-3) is a secondary multicomponent and is present in an amount of 15 to 45% by weight, more particularly 20 to 40% by weight, especially 28 to 39.5% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). Compound (I-1) is in particular a secondary compound and is present in an amount of 0.1 to 10% by weight, more particularly 0.5 to 5% by weight, especially 0.5 to 2% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). Of course, the percentages of compounds (I-1), (I-2) and (I-3) add up to 100%.

[0071] In another specific embodiment of the ternary mixture of compounds (I-1), (I-2) and (I-3), compound (I-3) is predominant. In particular, it is present in an amount of 50 to 90% by weight, more particularly 55 to 90% by weight, especially 55 to 85% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). In particular, in the ternary mixture, compound (I-2) is a secondary multicomponent and is present in an amount of 9 to 45% by weight, more particularly 9 to 44.5% by weight, especially 13 to 44.5% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). Compound (I-1) is in particular a secondary compound and is present in an amount of 0.1 to 10% by weight, more particularly 0.5 to 5% by weight, especially 0.5 to 2% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). Of course, the percentages of compounds (I-1), (I-2) and (I-3) add up to 100%.

[0072] Specifically, the mixture contains compounds I-1, I-2 and I-3, wherein relative to the total weight of compounds I-1, I-2 and I-3, compound I-1 is contained in an amount of 0.5 to 1.5 weight %, compound I-2 is contained in an amount of 15 to 73.5 weight %, and compound I-3 is contained in an amount of 25 to 84.5 weight %. Of course, the percentages of compounds (I-1), (I-2) and (I-3) add up to 100%.

[0073] As stated, in a mixture of at least two of such compounds (I-1), (I-2) and (I-3), X preferably has the same meaning in all compounds (I-1), (I-2), (I-3) contained in the mixture.

[0074] In another preferred embodiment of the present invention, in the compounds of general formula (I), R 1 is hydrogen [Compound (I) is therefore Compound (I-4)].

[0075] In another preferred embodiment of the present invention, in the compounds of general formula (I), R 1 is OH [Compound (I) is therefore Compound (I-5)].

[0076] In another preferred embodiment of the present invention, in the compounds of general formula (I), R 1 is O-C1-C4-alkyl [Compound (I) is therefore Compound (I-6)]. In particular, R 1 is O-C1-C2-alkyl (i.e. R 1 is methoxy or ethoxy). Specifically, R 1 It's a methoxy group.

[0077] In another preferred embodiment of the present invention, in the compounds of general formula (I), R 1 O-(C=O)-R 5 [Compound (I) is therefore compound (I-7)] Preferably, R 5 is C1-C4-alkyl, in particular C1-C2-alkyl. 5 is a methyl group (i.e. R 1 is acetoxy).

[0078] However, more preferably, the compound of formula (I) is compound (I-1) wherein R 2 With R 1 together represent a double bond, or a compound (I-2) in which R 3 With R 1 together represent a double bond, or a compound (I-3) in which R 4 With R 1 together represent a double bond, or a mixture of at least two compounds (I-1), (I-2) and (I-3) (wherein compound (I-1), compound (I-2), compound (I-3) or a mixture of at least two compounds (I-1), (I-2) and (I-3) may contain a minor amount of 1 is a compound I) wherein R 1 is hydrogen; or a compound (I) wherein R 1 is a compound (I) wherein R1 In particular, the compound of formula (I) is compound (I-1) wherein R 2 With R 1 together represent a double bond, or a compound (I-2) in which R 3 With R 1 together represent a double bond, or a compound (I-3) in which R 4 With R 1 together represent a double bond, or a mixture of at least two compounds (I-1), (I-2) and (I-3) (wherein compound (I-1), compound (I-2), compound (I-3) or a mixture of at least two compounds (I-1), (I-2) and (I-3) may contain a minor amount of 1 is a compound I) wherein R 1 is hydrogen; or a compound (I) wherein R 1 Specifically, the compound of formula (I) is compound (I-1), wherein R 2 With R 1 together represent a double bond, or a compound (I-2) in which R 3 With R 1 together represent a double bond, or a compound (I-3) in which R 4 With R 1 together represent a double bond, or a mixture of at least two compounds (I-1), (I-2) and (I-3) (wherein compound (I-1), compound (I-2), compound (I-3) or a mixture of at least two compounds (I-1), (I-2) and (I-3) may contain a minor amount of 1 The above mixture is preferably a mixture of double bond isomers, wherein X in all compounds (I) contained therein has the same meaning.

[0079] In a particular embodiment of the invention, in the compounds of formula (I), X is O and R 2 , R 3 , R 4 One and R 1 together represent a double bond.

[0080] In a more specific embodiment, the compound of formula (I) is compound (I-1), wherein R 2 With R 1 together represent a double bond and wherein X is O, or is compound (I-2) wherein R 3 With R 1 together represent a double bond and wherein X is O, or is a compound (I-3) wherein R 4 With R 1Together represent a double bond and wherein X is O, or a mixture of at least two compounds (I-1), (I-2) and (I-3) wherein X is O. As described above, compound (I-1), compound (I-2), compound (I-3) or a mixture of at least two compounds (I-1), (I-2) and (I-3) may contain a minor amount of 1 The term "minor amount" means less than 3% by weight, preferably less than 1% by weight, relative to compounds (I-1), (I-2) and (I-3) or mixtures thereof, including compounds wherein R 1 is based on the total weight of compound I containing OH.

[0081] In a more specific embodiment, the compound of formula (I) is compound (I-1), wherein R 2 With R 1 together represent a double bond and X is O. In another more specific embodiment, the compound of formula (I) is compound (I-2), wherein R 3 With R 1 together represent a double bond and X is O. In another more specific embodiment, the compound of formula (I) is compound (I-3), wherein R 4 With R 1 Together represent a double bond and X is O. Specifically, the compound of formula (I) is compound (I-2) wherein X is O.

[0082] In yet another more specific embodiment, the compound of formula (I) is a mixture of at least two compounds (I-1), (I-2) and (I-3), wherein X is O at each occurrence. More particularly, the mixture contains compounds (I-2) and (I-3) or contains all three compounds (I-1), (I-2) and (I-3), wherein X is O at each occurrence.

[0083] In particular, the mixture contains compounds I-2 and I-3 and optionally also compound I-1, wherein X is O in each case; wherein compound I-1 is contained in an amount of 0 to 10% by weight, compound I-2 is contained in an amount of 1 to 80% by weight, and compound I-3 is contained in an amount of 15 to 99% by weight, relative to the total weight of compounds I-1, I-2 and I-3. Specifically, the mixture contains all three compounds (I-1), (I-2) and (I-3), wherein X is O in each case; wherein compound I-1 is contained in an amount of 0.1 to 10% by weight, compound I-2 is contained in an amount of 1 to 79.9% by weight, and compound I-3 is contained in an amount of 15 to 99% by weight, relative to the total weight of compounds I-1, I-2 and I-3.

[0084] In a specific embodiment, the compound of formula (I) is a binary mixture of compounds (I-2) and (I-3), wherein X is in each case O and wherein compound (I-3) is predominant, i.e. it is present in an amount of more than 50% by weight, based on the weight of the mixture consisting of compounds (I-2) and (I-3). In particular, it is present in an amount of 70 to 99% by weight, more particularly 75 to 98% by weight, especially 80 to 95% by weight, very especially 90 to 95% by weight, based on the weight of the mixture consisting of compounds (I-2) and (I-3); the difference to 100% is compound (I-2).

[0085] In a specific embodiment, the compound of formula (I) is a ternary mixture of compounds (I-1), (I-2) and (I-3), wherein X is in each case O and wherein compound (I-2) is predominant. In particular, it is present in an amount of 50 to 80% by weight, more particularly 55 to 75% by weight, especially 60 to 70% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). In particular, in the ternary mixture, compound (I-3) is a secondary multicomponent and is present in an amount of 15 to 45% by weight, more particularly 20 to 40% by weight, especially 28 to 39.5% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). Compound (I-1) is especially a minor compound and is present in an amount of 0.1 to 10% by weight, more especially 0.5 to 5% by weight, especially 0.5 to 2% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). Of course, the percentages of compounds (I-1), (I-2) and (I-3) add up to 100%.

[0086] In another specific embodiment, the compound of formula (I) is a ternary mixture of compounds (I-1), (I-2) and (I-3), wherein X is in each case O and wherein compound (I-3) is predominant. In particular, it is present in an amount of 50 to 90% by weight, more particularly 70 to 90% by weight, especially 75 to 85% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). In particular, in the ternary mixture, compound (I-2) is a minor multicomponent and is present in an amount of 9 to 45% by weight, more particularly 9 to 29.5% by weight, especially 13 to 24.5% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). Compound (I-1) is especially a minor compound and is present in an amount of 0.1 to 10% by weight, more especially 0.5 to 5% by weight, especially 0.5 to 2% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). Of course, the percentages of compounds (I-1), (I-2) and (I-3) add up to 100%.

[0087] Specifically, the mixture contains compounds I-1, I-2 and I-3, wherein X is O in each case, wherein compound I-1 is contained in an amount of 0.5 to 1.5% by weight, compound I-2 is contained in an amount of 15 to 73.5% by weight, and compound I-3 is contained in an amount of 25 to 84.5% by weight, relative to the total weight of compounds I-1, I-2 and I-3. Of course, the percentages of compounds (I-1), (I-2) and (I-3) add up to 100%.

[0088] In another preferred embodiment of the present invention, in the compounds of general formula (I), R 1 is hydrogen and X is O (compound (I) is therefore compound (I-4) wherein X is O).

[0089] In another preferred embodiment of the present invention, in the compounds of general formula (I), R 1 is OH and X is O (compound (I) is therefore compound (I-5) wherein X is O).

[0090] In another preferred embodiment of the present invention, in the compounds of general formula (I), R 1 is O-C1-C4-alkyl and X is O (compound (I) is therefore compound (I-6) wherein X is O). In particular, R 1 is O-C1-C2-alkyl (i.e. R 1 is methoxy or ethoxy) and X is O. Specifically, R 1 is methoxy and X is O.

[0091] In another preferred embodiment of the present invention, in the compounds of general formula (I), R 1 O-(C=O)-R 5 and X is O (Compound (I) is therefore Compound (I-7) wherein X is O). Preferably, R 5 is C1-C4-alkyl, in particular C1-C2-alkyl, and X is O. In particular, R 5 is a methyl group (i.e. R 1 is acetoxy) and X is O.

[0092] However, more preferably, the compound of formula (I) is compound (I-1) wherein R 2 With R 1 together represent a double bond and X is O, or is a compound (I-2) in which R 3 With R 1 together represent a double bond and X is O, or is a compound (I-3) in which R 4 With R 1 together represent a double bond and X is O, or a mixture of at least two compounds (I-1), (I-2) and (I-3), wherein X is O in each case (wherein compound (I-1), compound (I-2), compound (I-3) or a mixture of at least two compounds (I-1), (I-2) and (I-3) may contain minor amounts of 1 is OH and X is O); or a compound wherein R 1 is hydrogen and X is O; or a compound (I) wherein R 1 is OH and X is O; or a compound (I) wherein R 1 is methoxy and X is O. In particular, the compound of formula (I) is compound (I-1) wherein R 2 With R 1 together represent a double bond and X is O, or is a compound (I-2) in which R 3 With R 1 together represent a double bond and X is O, or is a compound (I-3) in which R 4 With R 1 together represent a double bond and X is O, or a mixture of at least two compounds (I-1), (I-2) and (I-3), wherein X is O in each case (wherein compound (I-1), compound (I-2), compound (I-3) or a mixture of at least two compounds (I-1), (I-2) and (I-3) may contain minor amounts of 1 is OH and X is O); or a compound wherein R 1 is hydrogen and X is O; or a compound (I) wherein R 1is OH and X is O. Specifically, the compound of formula (I) is compound (I-1) wherein R 2 With R 1 together represent a double bond and X is O, or is a compound (I-2) in which R 3 With R 1 together represent a double bond and X is O, or is a compound (I-3) in which R 4 With R 1 together represent a double bond and X is O, or a mixture of at least two compounds (I-1), (I-2) and (I-3), wherein X is O in each case (wherein compound (I-1), compound (I-2), compound (I-3) or a mixture of at least two compounds (I-1), (I-2) and (I-3) may contain minor amounts of 1 is OH and X is O compound I).

[0093] In another specific embodiment of the invention, in the compounds of formula (I), X is S and R 2 , R 3 , R 4 One and R 1 together represent a double bond.

[0094] In another more specific embodiment, the compound of formula (I) is compound (I-1), wherein R 2 With R 1 together represent a double bond and wherein X is S, or is compound (I-2) wherein R 3 With R 1 together represent a double bond and wherein X is S, or is compound (I-3) wherein R 4 With R 1 Together represent a double bond and wherein X is S, or a mixture of at least two compounds (I-1), (I-2) and (I-3) wherein X is S. As described above, compound (I-1), compound (I-2), compound (I-3) or a mixture of at least two compounds (I-1), (I-2) and (I-3) may contain a minor amount of 1 The term "minor amount" means less than 3% by weight, preferably less than 1% by weight, relative to compounds (I-1), (I-2) and (I-3) or mixtures thereof, including compounds wherein R 1 is based on the total weight of compound I containing OH.

[0095] In another more specific embodiment, the compound of formula (I) is compound (I-1), wherein R 2 With R 1together represent a double bond and X is S. In another more specific embodiment, the compound of formula (I) is compound (I-2), wherein R 3 With R 1 together represent a double bond and X is S. In another more specific embodiment, the compound of formula (I) is compound (I-3), wherein R 4 With R 1 Together represent a double bond and X is S. Specifically, the compound of formula (I) is compound (I-2) wherein X is S.

[0096] In a further specific embodiment, the compound of formula (I) is a mixture of at least two compounds (I-1), (I-2) and (I-3), wherein X is S in each case. More particularly, the mixture contains compounds (I-2) and (I-3) or contains all three compounds (I-1), (I-2) and (I-3), wherein X is S in each case.

[0097] In particular, the mixture contains compounds I-2 and I-3 and optionally also compound I-1, wherein X is S in each case; wherein compound I-1 is contained in an amount of 0 to 10% by weight, compound I-2 is contained in an amount of 1 to 80% by weight, and compound I-3 is contained in an amount of 15 to 99% by weight, relative to the total weight of compounds I-1, I-2 and I-3. Specifically, the mixture contains all three compounds (I-1), (I-2) and (I-3), wherein X is S in each case; wherein compound I-1 is contained in an amount of 0.1 to 10% by weight, compound I-2 is contained in an amount of 1 to 79.9% by weight, and compound I-3 is contained in an amount of 15 to 99% by weight, relative to the total weight of compounds I-1, I-2 and I-3.

[0098] In a specific embodiment, the compound of formula (I) is a binary mixture of compounds (I-2) and (I-3), wherein X in each case is S and wherein compound (I-3) is predominant, i.e. it is present in an amount of more than 50% by weight, based on the weight of the mixture consisting of compounds (I-2) and (I-3). In particular, it is present in an amount of 50 to 99% by weight, more particularly 55 to 90% by weight, especially 55 to 80% by weight, based on the weight of the mixture consisting of compounds (I-2) and (I-3); the difference to 100% is compound (I-2).

[0099] In a specific embodiment, the compound of formula (I) is a ternary mixture of compounds (I-1), (I-2) and (I-3), wherein X in each case is S and wherein compound (I-3) is predominant. In particular, it is present in an amount of 50 to 80% by weight, more particularly 55 to 75% by weight, especially 55 to 70% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). In particular, in the ternary mixture, compound (I-2) is a secondary multicomponent and is present in an amount of 10 to 45% by weight, more particularly 20 to 44.5% by weight, especially 25 to 43% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). Compound (I-1) is especially a minor compound and is present in an amount of 0.1 to 10% by weight, more especially 0.5 to 5% by weight, especially 0.5 to 2% by weight, based on the weight of the mixture consisting of compounds (I-1), (I-2) and (I-3). Of course, the percentages of compounds (I-1), (I-2) and (I-3) add up to 100%.

[0100] In another preferred embodiment of the present invention, in the compounds of general formula (I), R 1 is hydrogen and X is S (compound (I) is therefore compound (I-4) wherein X is S).

[0101] In another preferred embodiment of the present invention, in the compounds of general formula (I), R 1 is OH and X is S (compound (I) is therefore compound (I-5) wherein X is S).

[0102] In another preferred embodiment of the present invention, in the compounds of general formula (I), R 1 is O-C1-C4-alkyl and X is S (compound (I) is therefore compound (I-6) wherein X is S). In particular, R 1 is O-C1-C2-alkyl (i.e. R 1 is methoxy or ethoxy) and X is S. Specifically, R 1 is methoxy and X is S.

[0103] In another preferred embodiment of the present invention, in the compounds of general formula (I), R 1 O-(C=O)-R 5 and X is S (Compound (I) is therefore Compound (I-7) wherein X is S). Preferably, R 5 is C1-C4-alkyl, in particular C1-C2-alkyl, and X is S. In particular, R 5 is a methyl group (i.e. R 1 is acetoxy) and X is S.

[0104] However, more preferably, the compound of formula (I) is compound (I-1) wherein R 2 With R 1 together represent a double bond and X is S, or is compound (I-2) wherein R 3 With R 1 together represent a double bond and X is S, or is compound (I-3) wherein R 4 With R 1 together represent a double bond and X is S, or a mixture of at least two compounds (I-1), (I-2) and (I-3), wherein X is S in each case (wherein compound (I-1), compound (I-2), compound (I-3) or a mixture of at least two compounds (I-1), (I-2) and (I-3) may contain minor amounts of 1 is OH and X is S); or a compound wherein R 1 is hydrogen and X is S; or a compound (I) wherein R 1 Compound (I) wherein R is OH and X is S. In particular, the compound of formula (I) is compound (I-1) wherein R 2 With R 1 together represent a double bond and X is S, or is compound (I-2) wherein R 3 With R 1 together represent a double bond and X is S, or is compound (I-3) wherein R 4 With R 1 together represent a double bond and X is S, or a mixture of at least two compounds (I-1), (I-2) and (I-3), wherein X is S in each case (wherein compound (I-1), compound (I-2), compound (I-3) or a mixture of at least two compounds (I-1), (I-2) and (I-3) may contain minor amounts of 1 is OH and X is S); or a compound wherein R 1 is OH and X is S. Specifically, the compound of formula (I) is compound (I-1) wherein R 2 With R 1 together represent a double bond and X is S, or is compound (I-2) wherein R 3 With R 1 together represent a double bond and X is S, or is compound (I-3) wherein R 4 With R 1together represent a double bond and X is S, or a mixture of at least two compounds (I-1), (I-2) and (I-3), wherein X is S in each case (wherein compound (I-1), compound (I-2), compound (I-3) or a mixture of at least two compounds (I-1), (I-2) and (I-3) may contain minor amounts of 1 Compound I) wherein X is OH and X is S.

[0105] The compound of formula (I), its stereoisomers, mixtures of its stereoisomers and mixtures of two or more different compounds (I) are useful as aroma chemicals.

[0106] The term "aromachemical" refers to substances used to obtain a sensory impression, more precisely an olfactory or flavor impression, in particular a fragrance or flavor impression. The term "olfactory" refers to an odor impression without any positive or negative judgment, while the term "fragrance" (also called "perfume" or "scent") is associated with an odor impression that is generally perceived as pleasant. Flavours induce taste impressions.

[0107] "Pleasant odor", "pleasant odor impression", "pleasant olfactory properties", "sensory pleasant odor impression" and similar terms are hedonistic expressions that describe the niceness and conciseness of the odor impression presented by an aroma chemical. The more general hedonistic expression "favorable sensory properties" or "favorable organoleptic properties" describes the niceness and conciseness of the sensory impression presented by an aroma chemical. For the purposes of the present invention, the terms "sensory" and "sensory" refer to olfactory or flavor properties. "Niceness" and "conciseness" are terms familiar to those skilled in the art, perfumers. Niceness generally refers to a pleasant sensory impression that is spontaneously evoked, brings about a positive perception. However, "niceness" is not necessarily synonymous with "sweetness". "Niceness" can also be the smell of musk or sandalwood. "Conciseness" generally refers to a spontaneously evoked sensory impression that is reproducibly reminiscent of the same specific thing for the same test panel. For example, a substance may have an odor that spontaneously reminds one of "apple": the odor is then concisely "apple". If this apple smell is very pleasant, because it reminds one of, for example, a sweet, fully ripe apple, the smell is called "good". However, the smell of sour apples is usually also concise. If both reactions occur simultaneously when smelling the substance, in this example, a good and concise apple smell, then the substance has particularly favorable organoleptic properties.

[0108] The term "strong-smelling substances" refers to substances or aroma chemicals which exhibit a strong odor impression. A strong odor impression is understood to mean those properties of aroma chemicals which are clearly perceptible even at very low concentrations in the gas space. The intensity can be determined by means of a threshold determination. The threshold is the concentration of the substance in the relevant gas space at which a representative test panel just perceives an odor impression, but this threshold no longer has to be specified. Probably the strongest known class of substances (i.e. those with a very low odor threshold) are the mercaptans, whose thresholds are usually in the ppb / m 3 within the range.

[0109] Preferably, the compound of formula (I) as defined above or its mixture or its stereoisomer or its mixture of stereoisomers is used to present an olfactory impression. In particular, the compound of formula (I) as defined above or its mixture or its stereoisomer or its mixture of stereoisomers is used as a fragrance.

[0110] In particular, the mixture of the above compounds (I-1), (I-2) and (I-3) wherein X is O or a mixture of their stereoisomers is used to present white rosin, herbal, smoky, leather notes; or to produce an aroma with white rosin, herbal, smoky, leather notes. Specifically, the compounds (I-1), (I-2) and (I-3) wherein X is O are present in a weight ratio of about 1:65.5:33.5.

[0111] In particular, the mixture of the above compounds (I-1), (I-2) and (I-3) wherein X is O or a mixture of their stereoisomers is used to present herbal, smoky, spicy, nutmeg, galbanum, leather, oakmoss notes; or to produce an aroma having herbal, smoky, spicy, nutmeg, galbanum, leather, oakmoss notes. Specifically, the compounds (I-1), (I-2) and (I-3) wherein X is O are present in a weight ratio of about 1:19.5:79.5.

[0112] In particular, the mixture of the above compounds (I-2) and (I-3) wherein X is O or a mixture of their stereoisomers is used to present spicy, nutmeg, smoky, tobacco, leather, phenolic notes; or to produce an aroma with spicy, nutmeg, smoky, tobacco, leather, phenolic notes. Specifically, the compounds (I-2) and (I-3) wherein X is O are present in a weight ratio of 7:92.

[0113] In particular, the compound (I-2) wherein X is O or its stereoisomer or mixture of its stereoisomers is used to present rooty, galbanum, leathery, spicy notes; or to produce an aroma with rooty, galbanum, leathery, spicy notes.

[0114] In particular, where R 1 is H and X is O (of course R2 , R 3 and R 4 Compound (I) (=compound (I-4), wherein X=O) or its stereoisomers or mixtures of stereoisomers thereof, which is H), is used to present a smoky, lime, hickory, fresh (green), or sweet aroma; or to produce an aroma with smoky, lime, hickory, fresh (green), or sweet aroma.

[0115] In particular, where R 1 is OH and X is O (of course R 2 , R 3 and R 4 Compound (I) (=compound (I-5), wherein X=O) or its stereoisomers or mixtures of stereoisomers are used to present white rosin or floral notes; or to produce a fragrance with white rosin or floral notes.

[0116] In particular, where R 1 is OCH3 and X is O (of course R 2 , R 3 and R 4 The compound (I) or its stereoisomer or its mixture of stereoisomers is used to present a watery, melon-like, slightly bitter aroma; or to produce an aroma with a watery, melon-like, slightly bitter aroma.

[0117] In particular, the mixture of the above compounds (I-1), (I-2) and (I-3) or a mixture of their stereoisomers, wherein X is S, is used to present a fresh (green), herbal, chive, woody fragrance; or to produce an aroma with a fresh (green), herbal, chive, woody fragrance. Specifically, the compounds (I-1), (I-2) and (I-3) wherein X is S are present in a weight ratio of 1:39:60.

[0118] In particular, where R 1 is OH and X is S (of course R 2 , R 3 and R 4 Compound (I) (=compound (I-5), wherein X=S) or its stereoisomer or mixture of stereoisomers is used to present beer or burnt aroma; or to produce an aroma with beer or burnt aroma.

[0119] Compound (I), its mixture, its stereoisomer or its stereoisomer mixture is typically used in ready-to-use compositions, in particular perfuming ready-to-use compositions. "Perfuming ready-to-use compositions" as used herein refer to ready-to-use compositions which predominantly evoke a pleasant odor impression.

[0120] Perfumed ready-to-use compositions are, for example, compositions for personal care, for home care, for industrial applications, and also compositions for other applications, such as pharmaceutical compositions or crop protection compositions.

[0121] Preferably, compound (I), its mixture, its stereoisomer or its stereoisomer mixture is used in a composition selected from perfume compositions, body care compositions (including cosmetic compositions), oral dental hygiene products, hygiene products, cleaning compositions (including dishwashing compositions), fabric detergent compositions, compositions for diffusers, pharmaceutical compositions and crop protection compositions. Compound (I), its stereoisomer, its stereoisomer mixture or its double bond isomer is used as an aroma chemical in the above composition, preferably as a fragrance.

[0122] In particular, a mixture of the above compounds (I-1), (I-2) and (I-3) wherein X is O or a mixture of their stereoisomers is used to impart galbanum, herbal, smoky, leathery notes to the above compositions. Specifically, compounds (I-1), (I-2) and (I-3) wherein X is O are present in a weight ratio of about 1:65.5:33.5.

[0123] In particular, a mixture of the above compounds (I-1), (I-2) and (I-3) wherein X is O or a mixture of their stereoisomers is used to impart herbal, smoky, spicy, nutmeg, galbanum, leather, oakmoss notes to the above compositions. Specifically, compounds (I-1), (I-2) and (I-3) wherein X is O are present in a weight ratio of about 1:19.5:79.5.

[0124] In particular, a mixture of the above compounds (I-2) and (I-3) wherein X is O or a mixture of their stereoisomers is used to impart spicy, nutmeg, smoky, tobacco, leather, phenolic notes to the above compositions. Specifically, compounds (I-2) and (I-3) wherein X is O are present in a weight ratio of 7:92.

[0125] In particular, the compound (I-2) wherein X is O or its stereoisomer or mixture of stereoisomers thereof is used to impart rooty, galbanum, leathery, spicy notes to the above-listed compositions.

[0126] In particular, where R 1 is H and X is O (of course R 2 , R 3 and R 4 Compound (I) (=compound (I-4) wherein X=O) or its stereoisomers or mixtures of stereoisomers are used to impart smoky, lime, hickory, green, sweet notes to the above-listed compositions.

[0127] In particular, where R 1 is OH and X is O (of course R 2 , R 3 and R 4 Compound (I) (=compound (I-5) wherein X=O) or its stereoisomers or mixtures of stereoisomers are used to impart galbanum, floral notes to the above compositions.

[0128] In particular, where R 1 is OCH3 and X is O (of course R 2 , R 3 and R 4 Compound (I) or its stereoisomer or mixture of stereoisomers which is H) is used to impart a watery, melon-like, slightly bitter aroma to the above-listed compositions.

[0129] In particular, a mixture of the above compounds (I-1), (I-2) and (I-3) or a mixture of their stereoisomers, wherein X is S, is used to impart a fresh (green), herbal, chive, woody fragrance to the above compositions. Specifically, compounds (I-1), (I-2) and (I-3) wherein X is S are present in a weight ratio of 1:39:60.

[0130] In particular, where R 1 is OH and X is S (of course R 2 , R 3 and R 4 Compound (I) (=compound (I-5) wherein X=S) or its stereoisomers or mixtures of its stereoisomers which are H) are used to impart beer, burnt notes to the above-listed compositions.

[0131] Details regarding the above listed compositions are given below.

[0132] In addition to the olfactory properties, compound (I), its mixture, its stereoisomers or its stereoisomer mixture also exhibits advantageous secondary properties.

[0133] For example, they can provide better sensory attributes due to synergistic effects with other fragrances, which means that they can provide a boosting effect on other fragrances. They are therefore suitable as boosters for other fragrances.

[0134] Accordingly, another aspect of the present invention relates to the use of compound (I), its mixture, its stereoisomer or its stereoisomer mixture for modifying the aroma characteristics of a perfuming composition; more particularly to its use as an enhancer for other fragrances.

[0135] The strengthening effect means that the substance intensifies and intensifies the overall impression of the mixture in a fragrance preparation. For example, in the case of mint, it is known that menthyl methyl ether strengthens the aroma or flavoring mixture of mint oil, especially in the top notes, bringing about a significantly stronger and more complex sensation, although the ether itself, as a pure substance, does not produce a particularly strong odor at all. In fragrance applications, as a pure substance, it only exhibits a light jasmine note. (Methyl dihydrojasmonate) as an odor enhancer enhances the spread, freshness and volume of perfume compositions. The enhancement effect is particularly desirable when a top note character is desired in applications where the odor impression is to be delivered particularly quickly and intensely, such as in deodorants, air fresheners or in the taste field in chewing gum.

[0136] To achieve such a boosting effect, compound (I), its mixture, its stereoisomer or its stereoisomer mixture is usually used in an amount of 0.1-20% by weight, preferably 0.5 to 5% by weight, in particular 0.6 to 3% by weight, based on the total weight of the fragrance mixture.

[0137] In addition, compound (I), its mixture, its stereoisomer or its stereoisomer mixture may have further positive effects on the composition in which they are used. For example, they may enhance the overall performance of the composition into which they are incorporated, such as stability, for example, the formulation stability, extensibility or durability of the composition.

[0138] In another aspect, the present invention relates to an aroma chemical composition comprising compound (I), a mixture thereof, a stereoisomer thereof or a mixture of stereoisomers thereof. The term "aroma chemical composition" as used herein refers to a composition that induces a pleasant odor impression.

[0139] Preferably, the aroma chemical composition comprises

[0140] - a compound of formula (I) or a mixture thereof [ie a mixture of different compounds (I)] or a stereoisomer thereof or a mixture of stereoisomers thereof; and

[0141] at least one additional fragrance chemical and / or at least one non-fragrance chemical carrier, wherein the non-fragrance chemical carrier is in particular selected from surfactants, oil components (emollients) and solvents.

[0142] The additional aroma chemical is of course other than a compound of formula (I) or a stereoisomer thereof or a mixture of stereoisomers thereof.

[0143] By virtue of their physical properties, the compounds of formula (I), their mixtures, their stereoisomers or their stereoisomer mixtures have particularly good, almost universal solvent properties for other fragrances and other conventional ingredients in ready-to-use perfuming compositions, in particular for example perfume compositions. They can therefore be combined intensively with other aroma chemicals, thereby making it possible in particular to create perfume compositions with novel and advantageous sensory properties. In particular, as already explained above, they can provide a boosting effect on other fragrances.

[0144] Accordingly, in a preferred embodiment, the aroma chemical composition comprises a compound of formula (I) as defined above, or a mixture thereof, or a stereoisomer thereof, or a mixture of stereoisomers thereof; and at least one additional aroma chemical.

[0145] The additional aroma chemicals may be, for example, one, preferably 2, 3, 4, 5, 6, 7, 8 or more aroma chemicals selected from the following:

[0146] Geranyl acetate (3,7-dimethyl-2,6-octadien-1-yl acetate), α-hexylcinnamaldehyde, 2-phenoxyethyl isobutyrate (Phenirat 1 ), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), methyl dihydrojasmonate (preferably having a cis isomer content of 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 2a ), cinnamyl alcohol, 4,7-methylene-3a,4,5,6,7,7a-hexahydro-5-indenyl acetate and / or 4,7-methylene-3a,4,5,6,7,7a-hexahydro-6-indenyl acetate (Herbaflorat 1 ), citronellol, citronellol acetate, tetrahydrogeraniol, vanillin, linalyl acetate, styrol acetate (1-phenylethyl acetate), octahydro-2,3,8,8-tetramethyl-2-naphthone 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-butyl cyclohexyl acetate (Oryclone 1 ), 2-tert-butyl cyclohexyl acetate (Agrumex HC 1), α-ionone (4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3-butene-2-one), n-α-methylionone, α-isomethylionone, coumarin, terpineol acetate, 2-phenylethyl alcohol, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde (Lyral 3 ), α-amylcinnamaldehyde, ethylene glycol brazilate, (E)- and / or (Z)-3-methylcyclopentadeca-5-enone (Muscenon 9 ), 15-pentadeca-11-ene lactone and / or 15-pentadeca-12-ene lactone (Globalide 1 ), 15-cyclopentadecalactone (Macrolide 1 )、1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthyl)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-butene-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-heptene-1-aldehyde (Melonal 2 ), borneol, 3-(3-isopropylphenyl)butyraldehyde (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 70% by weight or more), and 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydronaphthalen-2-ol (Ambrinol S 1 ). In the present invention, the above-mentioned aroma chemicals are correspondingly preferably combined with the compound of formula (I) as defined above or its stereoisomer or mixture of stereoisomers or double bond isomers thereof.

[0147] A further embodiment of the present invention relates to a composition comprising a compound of formula (I) as defined above or a mixture thereof or a stereoisomer thereof or a mixture of stereoisomers thereof and at least one additional aroma chemical selected from methyl benzoate, benzyl acetate, geranyl acetate, 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol and linalool.

[0148] A further embodiment of the present invention relates to a composition comprising a compound of formula (I) as defined above or a mixture thereof or a stereoisomer thereof or a mixture of stereoisomers thereof and 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol.

[0149] A further embodiment of the present invention relates to a composition comprising a compound of formula (I) or a mixture thereof or a stereoisomer thereof or a mixture of stereoisomers thereof as defined above and methyl benzoate.

[0150] Where trade names are given above, these refer to the following sources:

[0151] 1 A trading name of Symrise GmbH, Germany;

[0152] 2 Trade name of Givaudan AG, Switzerland;

[0153] 2a Trade name of BASF SE, Germany;

[0154] 3 Trade name of International Flavors & Fragrances Inc., USA;

[0155] 5 A trading name of Danisco Seillans SA, France;

[0156] 9 A trading name of Firmenich SA, Switzerland;

[0157] 10 A trading name of PFW Aroma Chemicals BV, the Netherlands.

[0158] Additional aroma chemicals with which compounds of formula (I) as defined above or mixtures thereof or stereoisomers or mixtures of stereoisomers thereof can be combined, for example to produce compositions according to the invention, can be found, for example, in S. Arctander, Perfume and Flavor Chemicals, Vol. I and II, Montclair, NJ, 1969, self-published or in K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4th edition, Wiley-VCH, Weinheim 2001. In particular, mention may be made of:

[0159] Extracts from natural raw materials, such as essential oils, concretes, absolutes, resins, resinoids, balsams, tinctures, e.g.

[0160] Ambergris tincture; Balsam oil; Angelica seed oil; Angelica root oil; Anise oil; Valerian oil; Basil oil; Moss absolute; Bay oil; Wormwood oil; Benzoin resin; Bergamot oil; Beeswax absolute; Birch tar; Bitter almond oil; Celery oil; Buchu leaf oil; Brazilian sandalwood oil; Juniper tar; Calamus oil; Camphor oil; Ylang ylang oil; Cardamom oil; Caraway oil; Cinnamon oil; Cinnamon absolute; Castoreum absolute; Cedar leaf oil; Cedarwood oil; Cistus oil; Citronella oil; Lemon oil; Copaiba balsam; Copaiba balsam oil; Coriander oil; Costus root oil; Kumin oil; Cypress oil; Davana oil; Dill leaf oil; Dill seed oil; Eau de brouts absolute; oakmoss absolute; elemi resin oil; tarragon oil; lemon eucalyptus oil; eucalyptus oil; fennel oil; pine needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiac wood oil; guarana resin; guarana balsam oil; helichrysum absolute; helichrysum oil; ginger oil; orris root absolute; orris root oil; jasmine absolute; sweet calamus oil; blue chamomile oil; Roman chamomile oil; carrot seed oil; quinoa oil; pine needle oil; spearmint Oil; Artemisia annua oil; Lavender oil; Lavender absolute; Lavender resin; Lavender absolute; Lavender oil; Lemongrass oil; Angelica dahurica oil; Lime oil distilled; Lime oil pressed; Camphor oil; Litsea cubeba oil; Bay leaf oil; Nutmeg oil; Origanum vulgare oil; Mandarin oil; Cinnamon bark oil; Mimosa absolute; Musk seed oil; Musk tincture; Sage oil; Nutmeg oil; Myrrh absolute; Myrrh Oil; Myrtle Oil; Clove Leaf Oil; Clove Flower Oil; Neroli Oil; Frankincense Absolute; Frankincense Oil; Red Myrrh Oil; Neroli Absolute; Orange Oil; Oregano Oil; Palmarosa Oil; Patchouli Oil; Perilla Seed Oil; Peru Balsam Oil; Parsley Leaf Oil; Parsley Seed Oil; Petitgrain Oil; Peppermint Oil; Pepper Oil; Allspice Seed Oil; Pine Oil; Peppermint Oil; Rose Absolute; Rosewood Oil; Rose Oil; Rosemary Oil; Sage Oil; Spanish Sage Oil ; sandalwood oil; celery seed oil; spike lavender oil; star anise oil; styrax oil; marigold oil; fir leaf oil; tea tree oil; turpentine oil; thyme oil; tolu balsam; tonka bean absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniper berry oil; lees oil; wormwood oil; wintergreen oil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil, and fractions thereof, or components isolated therefrom;

[0161] Individual essences selected from 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;

[0162] Aliphatic alcohols, for example hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)-3-hexenols; 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;

[0163] Aliphatic aldehydes and acetals thereof, for example, 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 acetal (heptanal diethylacetal); 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde; (E / Z)-1-(1-methoxypropoxy)-hex-3-ene; aliphatic ketones and their oximes, for example 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;

[0164] Aliphatic sulfur compounds, such as 3-methylthiohexanol; 3-methylthiohexanol acetate; 3-mercaptohexanol; 3-mercaptohexanol acetate; 3-mercaptohexanol butyrate; 3-acetylthiohexanol acetate; 1-menthene-8-thiol;

[0165] Aliphatic nitriles, for example 2-nonenenitrile; 2-undecenenitrile; 2-tridecenenitrile; 3,12-tridecadienenitrile; 3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl-6-octenenitrile;

[0166] Esters of aliphatic carboxylic acids, for example (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-octynoate; methyl 2-nonynoate; allyl 2-isopentyloxyacetate; methyl-3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl crotonate;

[0167] acyclic terpene alcohols, for example 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, valerates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates;

[0168] 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; geranylacetone; and the dimethyl- and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal; cyclic terpene alcohols, such as menthol; isopulegol; alpha-terpineol; terpine-4-ol; menth-8-ol; menth-1-ol; menth-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetivol; guaiacol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates;

[0169] Cyclic terpene aldehydes and ketones, for example menthone; isomenthone; 8-mercaptomenth-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-damascone; δ-damascone; γ-damascone; 1-(2,4,4-trimethyl- 2-cyclohexen-1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methylenenaphthalene-8(5H)-one; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; oleanone; dihydrooleanone; 4,6,8-megatrien-3-one; α-orangealdehyde; β-orangealdehyde; acetylated cedarwood oil (methyl cedarwood ketone);

[0170] Cyclic alcohols, for example 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isoborneolcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

[0171] 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-butene-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-butene-1-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-butene-1-ol; -(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;

[0172] Cyclic and alicyclic ethers, for example eucalyptol; cedarwood methyl ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclododecane; α-cedarwood oxide; 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;

[0173] Cyclic and macrocyclic ketones, for example 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-cyclohexadecene-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 8-cyclohexadecene-1-one; 7-cyclohexadecene-1-one; (7 / 8)-cyclohexadecene-1-one; 9-cycloheptadecene-1-one; cyclopentadecanone; cyclohexadecanone;

[0174] Cycloaliphatic aldehydes, for example 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarboxaldehyde;

[0175] Alicyclic ketones, for example 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-naphthylmethyl ketone; methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl(2,4-dimethyl-3-cyclohexen-1-yl)ketone;

[0176] Esters of cyclic alcohols, such as 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-amylcyclohexyl acetate; 4-tert-amylcyclohexyl 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 ester; 4,7-methylene-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate; 4,7-methylene-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate; 4,7-methylene-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate; 4,7-methyleneoctahydro-5 or 6-indenyl acetate;

[0177] Esters of cycloaliphatic alcohols, for example 1-cyclohexylethyl crotonate;

[0178] Esters of cycloaliphatic carboxylic acids, for example 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;

[0179] Aromatic aliphatic alcohols, for example benzyl alcohol; 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethanol; 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;

[0180] Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, for example 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;

[0181] Aromatic aliphatic ethers, for example 2-phenethyl methyl ether; 2-phenethyl isopentyl ether; 2-phenethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; 2-phenylpropanal dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9b-tetrahydroindenyl[1,2-d]-m-dioxine; 4,4a,5,9b-tetrahydro-2,4-dimethylindenyl[1,2-d]-m-dioxine;

[0182] Aromatic and aromatic aliphatic aldehydes, for example benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; 2-phenylpropanal; 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;

[0183] Aromatic and araliphatic ketones, for example acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthyl)ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanylmethyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanylmethyl 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-naphthylacetonone;

[0184] Aromatic and araliphatic carboxylic acids and their esters, for example benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isopentyl 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;

[0185] Nitrogen-containing aromatic compounds, for example 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-pentanenitrile; 3-methyl-5-phenylpentanenitrile; methyl anthranilate; methyl N-methyl anthranilate; the Schiff base of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;

[0186] Phenols, phenyl ethers and phenyl esters, for example estragole; anethole; eugenol; eugenol methyl ether; isoeugenol; isoeugenol 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-cresol phenylacetate;

[0187] Heterocyclic compounds, for example 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;

[0188] Lactones, such as 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decano-1,4-lactone; 1,4-undecalactone; 1,4-dodecalactone; 1,5-decanolide; 1,5-dodecalactone; 4-methyl-1,4-decanolide; 1,15-pentadecalactone; cis- and trans-11-pentadecene-1,15-lactone ; cis- and trans-12-pentadecen-1,15-lactone; 1,16-hexadecene-1,16-lactone; 9-hexadecene-1,16-lactone; 10-oxa-1,16-hexadecene-lactone; 11-oxa-1,16-hexadecene-lactone; 12-oxa-1,16-hexadecene-lactone; 1,12-dodecanediol glycol ester; 1,13-tridecanediol glycol ester; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin.

[0189] Advantageously, the sweet notes are enhanced by the combination with aroma chemicals having sweet notes, such as vanillin, 2,5-dimethyl-4-hydroxy-2H-furan-3-one (furanone) or 3-hydroxy-2-methyl-4H-pyran-4-one (maltol), by compound (I) or its stereoisomers or its double bond isomers.

[0190] A further aspect of the invention relates to a composition comprising a compound of formula (I) as defined above or a mixture thereof or a stereoisomer thereof or a mixture of stereoisomers thereof and at least one component selected from a surfactant, an emollient (oil component) and a solvent.

[0191] One embodiment of the present invention relates to a composition comprising a compound of formula (I) or a mixture thereof or a stereoisomer thereof or a mixture of stereoisomers thereof as defined above and at least one solvent.

[0192] In the present invention, a "solvent" is used to dilute the compound of formula (I) or the mixture thereof or its stereoisomer or its stereoisomer mixture as defined above used according to the invention without having its own olfactory properties. Some solvents also have immobilizing properties.

[0193] The one or more solvents can be present in the composition at 0.01 to 99% by weight of the composition. In a preferred embodiment of the present invention, the composition comprises 0.1 to 90% by weight of the composition, preferably 0.5 to 80% by weight of the solvent. The amount of the solvent can be selected according to the composition. In one embodiment of the present invention, the composition comprises 0.05 to 10% by weight of the composition, preferably 0.1 to 5% by weight, more preferably 0.2 to 3% by weight of the solvent. In one embodiment of the present invention, the composition comprises 20 to 70% by weight of the composition, preferably 25 to 50% by weight of the solvent.

[0194] 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).

[0195] Particularly preferred solvents are selected from ethanol, propylene glycol, dipropylene glycol, triethyl citrate, benzyl benzoate and isopropyl myristate.

[0196] In a preferred embodiment of the present invention, the solvent is selected from ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, triethyl citrate and isopropyl myristate.

[0197] According to another aspect, the compounds of formula (I), mixtures thereof, stereoisomers thereof or mixtures of stereoisomers thereof are suitable for use in surfactant-containing compositions. Due to their characteristic fragrance attributes, they are particularly useful for the perfuming of surfactant-containing compositions, such as detergents (particularly laundry care products and all-purpose cleaners).

[0198] One embodiment of the present invention therefore relates to a composition comprising a compound of formula (I) or a mixture thereof or a stereoisomer thereof or a mixture of stereoisomers thereof as defined above and at least one surfactant.

[0199] The surfactant may be selected from anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants. Surfactant-containing compositions, such as shower gels, foaming baths, shampoos, etc., preferably contain at least one anionic surfactant.

[0200] The composition according to the invention generally contains surfactants in an amount of 0 to 40% by weight, preferably 0 to 20% by weight, more preferably 0.1 to 15% by weight, in particular 0.1 to 10% by weight, based on the total weight of the composition. Typical examples of nonionic 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 methylals, optionally partially oxidized alkyl (alkenyl) 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. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional homolog distribution, although they preferably have a narrow range of homolog distribution.

[0201] Zwitterionic surfactants contain at least one quaternary ammonium group and at least one -COO (-) or -SO3 (-) Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinates, N-amidopropyl-N,N-dimethylammonium glycinates, for example cocoamidopropyldimethylammonium glycinates, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines, which contain 8 to 18 carbon atoms in the alkyl or acyl radical, and cocoamidoethylhydroxyethylcarboxymethylglycinate. The fatty acid amide derivatives known by the CTFA name cocoamidopropyl betaine are particularly preferred.

[0202] Amphoteric surfactants are also suitable, in particular as cosurfactants. Amphoteric surfactants are surface-active compounds which contain in the molecule, in addition to the C8 to C18 alkyl or acyl groups, at least one free amino group and at least one -COOH- or -SO3H- group and are capable of forming inner salts. Examples of suitable amphoteric surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acids and alkylaminoacetic acids, having approximately 8 to 18 carbon atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-cocoalk-ylaminopropionate, cocoacylaminoethylaminopropionate and acylsarcosine.

[0203] Anionic surfactants are characterized by a water-soluble anionic group, such as a carboxylate, sulfate, sulfonate or phosphate group, and a lipophilic group. Skin-safe anionic surfactants are known to practitioners in large quantities from relevant textbooks and are commercially available. They are, in particular, alkyl sulfates (in the form of their alkali metal, ammonium or alkanolammonium salts), alkyl ether sulfates, alkyl ether carboxylates, acyl isethionates, acyl sarcosinates, acyl taurines containing linear C12-18 alkyl or acyl groups, and sulfosuccinates and acyl glutamates (in the form of their alkali metal or ammonium salts).

[0204] Particularly suitable cationic surfactants are quaternary ammonium compounds, preferably ammonium halides, more particularly ammonium chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. In addition, readily biodegradable quaternary ammonium ester compounds, for example dialkylammonium methosulfates and methylhydroxyalkyldialkyloxyalkylammonium methosulfates sold under the name Stepantexe, and The corresponding products of the quaternary ammonium series can be used as cationic surfactants. "Esterquats" are generally understood to mean quaternized fatty acid triethanolamine ester salts. They can provide the composition with a particularly soft feel. They are known substances produced by relevant methods of organic chemistry. Other cationic surfactants that can be used according to the invention are quaternized protein hydrolysates.

[0205] One embodiment of the present invention relates to a composition comprising a compound of formula (I) as defined above, or a mixture thereof, or a stereoisomer thereof, or a mixture of stereoisomers thereof, and at least one oil component.

[0206] The oil component is generally present in a total amount of 0.1 to 80, preferably 0.5 to 70, more preferably 1 to 60, even more preferably 1 to 50, particularly 1 to 40, more particularly 5 to 25, especially 5 to 15% by weight of the composition.

[0207] The oil component can be selected, for example, from Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, and other additional esters such as myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl Suitable are isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate and erucyl erucate. Also suitable are C 18 -C 38 -alkyl-hydroxycarboxylic acid with a straight-chain or branched C6-C 22 - esters of fatty alcohols, more particularly dioctyl malate, esters of linear and / or branched fatty acids with polyols (for example propylene glycol, dimer glycol or trimer triol), 10 -Triglycerides of fatty acids, based on C6-C 18 -Liquid mono-, di- and triglyceride mixtures of fatty acids, C6-C 22 - esters of fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, more particularly benzoic acid, esters of dicarboxylic acids with polyols having 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, for example dicaprylyl carbonate (Cetiol@CC), Guerbet carbonates based on fatty alcohols having 6 to 18, preferably 8 to 10, carbon atoms, benzoic acid with linear and / or branched C6 to C 22 -Ester of alcohol (e.g. TN), linear or branched, symmetrical or asymmetrical dialkyl ethers containing 6 to 22 carbon atoms per alkyl group, such as dioctyl ether ( OE), ring-opening products of epoxidized fatty acid esters with polyols and hydrocarbons, or mixtures thereof.

[0208] The compounds of formula (I), mixtures thereof, stereoisomers thereof or mixtures of stereoisomers thereof as defined above can be used in a wide range of aroma chemical compositions. The olfactory properties of the compounds of formula (I), stereoisomers thereof, mixtures of stereoisomers thereof or double bond isomers thereof, the physical properties (such as solubility in conventional solvents and compatibility with other conventional ingredients of these compositions) and the toxicological acceptability determine their specific suitability for the intended use and composition.

[0209] Suitable aromachemical compositions are, for example, perfume compositions, body care compositions, oral-dental hygiene products, hygiene preparations, cleaning compositions, fabric detergent compositions, compositions for diffusers, pharmaceutical compositions and crop protection compositions.

[0210] The perfume composition may be chosen from fine fragrances, air fresheners in liquid form, gel form or applied to a solid carrier, aerosol sprays, scented cleansers, scented candles and oils, such as lamp oils or massage oils.

[0211] Examples of fine fragrances are perfume extracts, Eau de Parfums, Eau de Toilettes, Eau de Colognes, Eau de Solide and Extrait Parfum.

[0212] Body care compositions include cosmetic compositions and may be selected from aftershave products, preshave products, splashcolognes, 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, such as 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, self-tanning creams and lotions, hair care products, such as hair sprays, hair gels, setting hair lotions, conditioners, shampoos, permanent and semi-permanent hair colorants, hair styling compositions such as cold waves and hair softening compositions, hair tonics, hair creams and hair lotions. lotions, deodorants and antiperspirants, such as underarm sprays, roll-ons, deodorant sticks and deodorant creams, decorative cosmetics, such as eyeliner, eye shadow, nail polish, make-up, lipstick and mascara.

[0213] Oral dental hygiene products include, for example, toothpaste, dental floss, mouthwash, breath freshener, dental foam, dental gel, and dental strips.

[0214] The hygiene product may be selected from joss sticks, insecticides, insect repellents, propellants, rust removers, perfumed freshening wipes, armpit pads, baby diapers, sanitary napkins, toilet paper, cosmetic wipes, handkerchiefs, dishwasher deodorizers;

[0215] Cleaning compositions, such as solid surface cleaners, may be selected from perfumed acidic, alkaline and neutral cleaners, for example floor cleaners, window cleaners, dishwashing detergents for hand and machine washing, bathroom and sanitary cleaners, scouring milk, solid and liquid toilet cleaners, powder and foam carpet cleaners, waxes and polishes such as furniture polishes, floor waxes, shoe polishes, disinfectants, surface disinfectants and sanitary cleaners, brake disc cleaners, pipe cleaners, descaling agents, grill and oven cleaners, algae and moss removers, mildew removers, facade cleaners.

[0216] The fabric detergent composition may be selected from liquid detergents, powder detergents, laundry pretreaters such as bleaches, soaking agents and stain removers, fabric softeners, washing soaps, washing tablets.

[0217] Food means raw, cooked or processed edible substances, ice, beverages or ingredients used or intended for use, in whole or in part, for human consumption, or chewing gum, soft candy, jellies and sweets.

[0218] A dietary supplement is an edible product containing a dietary ingredient intended to further increase the nutritional value of the diet. A dietary ingredient may be one or any combination of the following: a vitamin, a mineral, a herb or other substance, an amino acid, a dietary substance used by humans to supplement the diet by increasing the total dietary intake, a concentrate, a metabolite, a component or an extract. A dietary supplement may be in many forms such as tablets, capsules, softgels, gelcaps, liquids or powders.

[0219] Pharmaceutical compositions include compositions intended for use in the diagnosis, cure, mitigation, treatment or prevention of disease, as well as preparations (other than food products) intended to affect the structure or any function of the human or other animal body.

[0220] Crop protection compositions comprise compositions intended for the management of plant diseases, weeds and other pests (vertebrates and invertebrates) that damage agricultural crops and forestry.

[0221] The composition according to the invention may further comprise one or more substances, for example: preservatives, abrasives, anti-acne agents, anti-skin aging agents, antibacterial agents, anti-cellulite agents, anti-dandruff agents, anti-inflammatory agents, anti-irritants, irritation reducing agents, antimicrobial agents, antioxidants, astringents, antiperspirants, preservatives, antistatic agents, binders, buffers, carrier materials, chelating agents, cell stimulants, cleaning agents, care agents, depilatories, surface active substances, deodorants, antiperspirants, emulsifiers, enzymes, essential oils, fibers, film formers, fixatives, foam formers, foam stabilizers, anti-foaming agents, foam boosters, fungicides, gelling agents, gel formers, hair care agents, hair fixatives, hair softeners, moisturizing agents, moisturizing substances, moisturizer substances, bleaching agents, strengtheners, stain removers, optical brighteners, impregnation agents, soil repellents, repellents, friction reducers, lubricants, moisturizers, ointments, opacifiers, plasticizers, covering agents, polishes, shine agents, polymers, powders, proteins, refatting agents, exfoliants, silicones, skin soothing agents, skin cleansers, skin care agents, skin healing agents, skin whitening agents, skin protectants, skin softeners, coolants, skin-cooling agents, warming agents, skin-warming agents, stabilizers, UV absorbers, UV filters, fabric softeners, suspending agents, skin tanning agents, thickeners, vitamins, oils, waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, alpha-hydroxy acids, polyhydroxy fatty acids, liquefiers, dyes, color protection agents, pigments, corrosion inhibitors, polyols, surfactants, electrolytes, organic solvents or silicone derivatives.

[0222] The compounds of formula (I) as defined above, their mixtures, their stereoisomers and mixtures of their stereoisomers, and the aromachemical compositions according to the present invention containing them can also be in microencapsulated form, spray-dried form, inclusion compound form or extruded product form. The properties can be further optimized in terms of more targeted aroma release by so-called "coating" with suitable materials, for which waxy synthetic substances, such as polyvinyl alcohol, are preferably used.

[0223] Microencapsulation can be carried out, for example, by means of capsule materials such as polyurethanes or soft gelatin by so-called coacervation methods. Spray-dried essential oils can be manufactured, for example, by spray-drying an emulsion or dispersion comprising a compound of formula (I) as defined above, a mixture of its stereoisomers, and a composition obtainable by the above method of the present invention, wherein available carrier materials are modified starch, protein, dextrin, and vegetable gum. Inclusion compounds can be prepared, for example, by introducing a dispersion of a flavor composition and a cyclodextrin or urea derivative into a suitable solvent, such as water. Compounds of formula (I) as defined above, their stereoisomers, mixtures of their stereoisomers, or compositions obtainable by the above method of the present invention can be melted together with a suitable waxy substance and extruded and then optionally solidified in a suitable solvent, such as isopropanol to manufacture extruded products.

[0224] Typically, the total amount of the compound of formula (I), its mixture, its stereoisomer or mixture of its stereoisomers in the aromachemical composition according to the invention is usually adapted to the specific intended use or intended application and can therefore vary within a wide range. Typically, the conventional standard commercial amount of perfume is used.

[0225] The composition according to the invention may comprise a total amount of 0.001 to 99.9% by weight, preferably 0.01 to 90% by weight, more preferably 0.05 to 80%, in particular 0.1 to 60% by weight, more particularly 0.1 to 40% by weight, for example 0.1 to 10% by weight or 0.1 to 15% by weight of a compound of formula (I) as defined above, a mixture thereof, a stereoisomer thereof or a mixture of stereoisomers thereof, based on the total weight of the composition.

[0226] In one embodiment of the invention, the composition comprises a compound of formula (I) as defined above, a mixture thereof, a stereoisomer thereof or a mixture of its stereoisomers in a total amount of 0.001 to 5 wt. %, preferably 0.01 to 2 wt. %, based on the total weight of the composition.

[0227] A further embodiment of the present invention relates to a method for preparing an aromachemical composition, in particular a perfuming composition, in particular a perfuming ready-to-use composition, comprising incorporating at least one compound of formula (I), a mixture thereof, a stereoisomer thereof or a mixture of stereoisomers thereof into a target composition, such as a ready-to-use composition, to produce an aromachemical composition, in particular a perfuming composition, in particular a perfuming ready-to-use composition. Alternatively, the present invention relates to a method for preparing an aromachemical composition, in particular a perfuming composition, in particular a perfuming ready-to-use composition, comprising mixing at least one compound of formula (I), a mixture thereof, a stereoisomer thereof or a mixture of stereoisomers thereof with at least one aromachemical different from compound (I) and / or with at least one non-aromatic chemical carrier. Suitable and preferred aromachemicals and non-aromatic chemical carriers different from compound (I) are described above.

[0228] For example, the process can be carried out by mixing at least one compound of formula (I), its stereoisomers or mixtures of stereoisomers as defined above and at least one additional compound chosen from aroma chemicals and non-aromatic chemical carriers different from compound (I).

[0229] The invention also relates to a method for modifying the aroma profile of an aromachemical composition, in particular a perfuming composition, in particular a perfuming ready-to-use composition, comprising incorporating into an aromachemical composition, in particular a perfuming composition, in particular a perfuming ready-to-use composition, at least one compound of formula (I), a mixture thereof, a stereoisomer thereof or a mixture of stereoisomers thereof.

[0230] In particular, the present invention relates to a process for preparing a perfume composition, a body care composition, an oral dental hygiene product, a hygienic article, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition or a crop protection composition, which comprises including a compound of formula (I) as defined above, a mixture thereof, a stereoisomer thereof or a mixture of stereoisomers thereof in the perfume composition, the body care composition, the oral dental hygiene product, the hygienic article, the cleaning composition, the fabric detergent composition, a composition for a diffuser, a pharmaceutical composition or a crop protection composition.

[0231] In one embodiment, the present invention relates to a method of imparting galbanum, herbal, smoky, leathery notes to a perfume composition, a body care composition, an oral dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition or a crop protection composition, comprising including a mixture of the above compounds (I-1), (I-2) and (I-3) wherein X is O, or a mixture of stereoisomers thereof, in the perfume composition, the body care composition, the oral dental hygiene product, the hygiene article, the cleaning composition, the fabric detergent composition, the composition for a diffuser, a pharmaceutical composition or a crop protection composition. Specifically, the compounds (I-1), (I-2) and (I-3) wherein X is O are present in a weight ratio of about 1:65.5:33.5.

[0232] In another embodiment, the present invention relates to a method of imparting herbal, smoky, spicy, nutmeg, galbanum, leather, oakmoss notes to a perfume composition, a body care composition, an oral dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition or a crop protection composition, comprising including a mixture of the above compounds (I-1), (I-2) and (I-3) wherein X is O, or a mixture of stereoisomers thereof, in the perfume composition, the body care composition, the oral dental hygiene product, the hygiene article, the cleaning composition, the fabric detergent composition, the composition for a diffuser, a pharmaceutical composition or a crop protection composition. Specifically, the compounds (I-1), (I-2) and (I-3) wherein X is O are present in a weight ratio of about 1:19.5:79.5.

[0233] In another embodiment, the present invention relates to a method of imparting spicy, nutmeg, smoky, tobacco, leather, phenolic notes to a perfume composition, a body care composition, an oral dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition or a crop protection composition, comprising including a mixture of the above compounds (I-2) and (I-3) wherein X is O or a mixture of their stereoisomers in the perfume composition, the body care composition, the oral dental hygiene product, the hygiene article, the cleaning composition, the fabric detergent composition, the composition for a diffuser, a pharmaceutical composition or a crop protection composition. Specifically, the compounds (I-2) and (I-3) wherein X is O are present in a weight ratio of 7:92.

[0234] In another embodiment, the present invention relates to a method of imparting a root, white rosin, leather, spicy note to a perfume composition, a body care composition, an oral dental hygiene product, a hygienic article, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition or a crop protection composition, comprising including a compound (I-2) wherein X is O or a stereoisomer thereof or a mixture of stereoisomers thereof in a perfume composition, a body care composition, an oral dental hygiene product, a hygienic article, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition or a crop protection composition.

[0235] In another embodiment, the present invention is a method of imparting a smoky, lime, hickory, green, sweet fragrance note to a perfume composition, a body care composition, an oral dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition, or a crop protection composition, comprising: 1 is H and X is O (of course R 2 , R 3 and R 4 Compound (I) (=compound (I-4), wherein X=O) or its stereoisomers or mixtures of stereoisomers, which is H) is included in perfume compositions, body care compositions, oral dental hygiene products, hygiene products, cleaning compositions, fabric detergent compositions, compositions for diffusers, pharmaceutical compositions or crop protection compositions.

[0236] In another embodiment, the present invention relates to a method of imparting galbanum, floral notes to a perfume composition, a body care composition, an oral dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition or a crop protection composition, comprising: 1 is OH and X is O (of course R 2 , R 3 and R 4 A compound of formula (I) (=compound (I-5), wherein X=O) or a stereoisomer thereof or a mixture of stereoisomers thereof is included in a perfume composition, a body care composition, an oral dental hygiene product, a hygiene product, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition or a crop protection composition.

[0237] In another embodiment, the present invention is a method of imparting a watery, melon-like, slightly bitter fragrance to a perfume composition, a body care composition, an oral dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition, or a crop protection composition, comprising: 1is OCH3 and X is O (of course R 2 , R 3 and R 4 The compound of formula (I) which is H) or its stereoisomer or mixture of stereoisomers is included in a perfume composition, a body care composition, an oral dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition or a crop protection composition.

[0238] In another embodiment, the present invention relates to a method of imparting a fresh, herbal, chive, woody note to a perfume composition, a body care composition, an oral dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition or a crop protection composition, comprising including a mixture of the above compounds (I-1), (I-2) and (I-3) or a mixture of stereoisomers thereof, wherein X is S, in the perfume composition, the body care composition, the oral dental hygiene product, the hygiene article, the cleaning composition, the fabric detergent composition, the composition for a diffuser, a pharmaceutical composition or a crop protection composition. Specifically, the compounds (I-1), (I-2) and (I-3) wherein X is S are present in a weight ratio of 1:39:60.

[0239] In another embodiment, the present invention relates to a method for imparting beer, burnt notes to a perfume composition, a body care composition, an oral dental hygiene product, a hygiene article, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition or a crop protection composition, comprising: 1 is OH and X is S (of course R 2 , R 3 and R 4 A compound of formula (I) (=compound (I-5), wherein X=S) or a stereoisomer thereof or a mixture of stereoisomers thereof, wherein X=S is H) is included in a perfume composition, a body care composition, an oral dental hygiene product, a hygiene product, a cleaning composition, a fabric detergent composition, a composition for a diffuser, a pharmaceutical composition or a crop protection composition.

[0240] In yet another aspect, the present invention relates to a compound of formula (Ia), a mixture thereof, a stereoisomer thereof or a mixture of stereoisomers thereof

[0241]

[0242] in

[0243] R 1 is hydrogen, OH, O-C1-C4-alkyl or O-(C=O)-R 5 ,

[0244] Where R 5 is selected from hydrogen and C1-C4-alkyl.

[0245] In particular, in compound (Ia), R 1 is selected from hydrogen, OH, methoxy, ethoxy and acetoxy. More particularly, R 1 is selected from hydrogen, OH and methoxy. 1 It is hydrogen or OH.

[0246] In an alternative specific embodiment of compound (Ia), R 1 is selected from OH, O-C1-C4-alkyl and O-(C=O)-R 5 ; Preferably selected from OH and O-C1-C4-alkyl; More preferably selected from OH, methoxy and ethoxy, especially selected from OH and methoxy.

[0247] In yet another aspect, the present invention relates to compounds of formula (Ib) or mixtures thereof, stereoisomers thereof or mixtures of stereoisomers thereof

[0248]

[0249] in

[0250] R 1 is hydrogen, OH, O-C1-C4-alkyl or O-(C=O)-R 5 ,

[0251] R 2 , R 3 , R 4 It is hydrogen;

[0252] or R 2 , R 3 , R 4 One and R 1 together they represent a double bond;

[0253] R 5 is selected from hydrogen and C1-C4-alkyl.

[0254] Preferably, in compound (Ib), R 2 With R 1 together represent a double bond, or R 3 With R 1 together represent a double bond, or R 4 With R 1 together represent a double bond, or compound (Ib) is a mixture of at least two such compounds; or in compound (Ib), R 1 is hydrogen or OH. In particular, in compound (Ib), R 2 With R1 together represent a double bond, or R 3 With R 1 together represent a double bond, or R 4 With R 1 together represent a double bond, or compound (Ib) is a mixture of at least two such compounds; or in compound (Ib), R 1 is OH. Specifically, in compound (Ib), R 2 With R 1 together represent a double bond, or R 3 With R 1 together represent a double bond, or R 4 With R 1 together represent a double bond, or compound (Ib) is a mixture of at least two such compounds. 2 With R 1 together represent a double bond, or R 3 With R 1 together represent a double bond, or R 4 With R 1 Compounds (Ib) which together represent a double bond, or a mixture of at least two such compounds, may contain a minor amount of 1 It is a compound of OH (Ib).

[0255] In another aspect, the invention relates to mixtures of at least two compounds of formula (I) as defined above.

[0256] In particular, the mixture is a mixture of at least two compounds I-1, I-2 and I-3, wherein in compound I-1 R 2 With R 1 Together they represent a double bond. In compound I-2, R 3 With R 1 together represent a double bond, and in compound I-3 R 4 With R 1 Together they represent a double bond. In such a mixture, X in all compounds I-1, I-2 and I-3 contained in the mixture preferably has the same meaning. Preferably, the mixture of I-1, I-2 and / or I-3 is a mixture containing compound I-2 and one or both of compounds I-1 and I-3; or a mixture containing compounds I-1 and I-2 and optionally also containing compound I-3; or a mixture containing compounds I-2 and I-3 and optionally also containing compound I-1; or a mixture containing compounds I-1, I-2 and I-3; and in particular a mixture containing compounds I-1 and I-2, wherein preferably, X in all compounds I-1, I-2 and I-3 contained in the mixture has the same meaning.

[0257] In another specific embodiment, the mixture contains compounds I-2 and I-3 and optionally also contains compound I-1. Specifically, the mixture contains compounds I-2 and I-3 and optionally also contains compound I-1, wherein relative to the total weight of compounds I-1, I-2 and I-3, compound I-1 is contained in an amount of 0 to 10% by weight, compound I-2 is contained in an amount of 1 to 80% by weight, and compound I-3 is contained in an amount of 15 to 99% by weight, wherein preferably, X in all compounds I-1, I-2 and I-3 contained in the mixture has the same meaning. More specifically, the mixture contains compounds I-1, I-2 and I-3, wherein relative to the total weight of compounds I-1, I-2 and I-3, compound I-1 is contained in an amount of 0.1 to 10% by weight, compound I-2 is contained in an amount of 1 to 79.9% by weight, and compound I-3 is contained in an amount of 15 to 99% by weight, wherein preferably, X in all compounds I-1, I-2 and I-3 contained in the mixture has the same meaning. Even more specifically, the mixture contains compounds I-1, I-2 and I-3, wherein relative to the total weight of compounds I-1, I-2 and I-3, compound I-1 is contained in an amount of 0.5 to 1.5% by weight, compound I-2 is contained in an amount of 15 to 73.5% by weight, and compound I-3 is contained in an amount of 25 to 84.5% by weight, wherein preferably, X in all compounds I-1, I-2 and I-3 contained in the mixture has the same meaning.

[0258] In a particular embodiment of the mixture according to the invention, X is S.

[0259] The compounds of formula (I) can be prepared by methods as described in the following schemes or in the description of the synthesis in the examples, or by standard methods of organic chemistry. If not otherwise specified, substituents, variables and indices are as defined above for formula (I).

[0260] More specifically, compound (I) can be prepared by a standard method for preparing cyclic ethers, for example, by the Prins reaction, which comprises reacting isoprenol (3-methylbut-3-en-1-ol) 1 with furfural (X=O) or thiophenecarboxaldehyde (X=S) 2 as shown in the following Scheme 1. The reaction of 1 with 2 is usually carried out under acidic conditions, for example, using hydrochloric acid, sulfuric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid or p-toluenesulfonic acid or using a polymer acid such as a strongly acidic cation exchanger. The term "strongly acidic cation exchanger" refers to a cation exchanger having a strongly acidic group. + The strongly acidic groups are usually sulfonic acid groups; they are usually bonded to a polymer matrix which can be, for example, in gel form or macroporous. Preference is given to styrene (co)polymers containing sulfonic acid groups, especially styrene-divinylbenzene copolymers containing sulfonic acid groups (e.g. SULFONATE® from Rohm and Haas). Brands of resins, such as 131). Further details are given below in the context of methods A and B. Suitably, the water formed in the reaction is usually removed by distillation to promote the reaction. The reaction is usually carried out in an organic solvent, especially if an acid different from an acidic cation exchanger is used. Suitable solvents are, for example, alkanes such as pentane or hexane, halogenated C1-C4-alkanes such as dichloromethane, chloroform or ethylene dichloride, cycloalkanes such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, aliphatic ethers such as diethyl ether, diisopropyl ether or methyl-tert-butyl ether, cyclic ethers such as tetrahydrofuran or dioxane, or carboxylic acid esters such as ethyl acetate. If an acidic cation exchanger is used, the reaction can also be neat, i.e. carried out without solvent.

[0261] 1 and 2 are usually applied in a molar ratio of 0.9:1 to 1.5:1, preferably in a molar ratio of 1:1 to 1.3:1. It is advantageous to use a slight excess of 1 to avoid the formation of acetal as a by-product, while if 2 is used in excess, acetal formation will be favored.

[0262] Further details are given below in the context of Methods A and B.

[0263] The reaction generally produces a crude product mixture containing 1 is OH (hereinafter referred to as I'), one or more of which R 2 , R 3 , R 4 One and R 1 The dashed lines are intended to indicate that one of the three dashed bonds is a double bond, while the other two are single bonds.

[0264] Process 1:

[0265]

[0266] If desired, compounds I' and I" can be separated from one another. If compound I" is a mixture of various double bond isomers, these can be separated from one another or enriched in one double bond isomer. Suitable separation and enrichment methods are known in the art and are, for example, distillation or chromatography.

[0267] If desired, the compound I" can be hydrogenated to a compound in which R 1 is compound I where H. Suitable hydrogenation conditions are described below in the context of methods A and B.

[0268] If desired, compound I' can be dehydrated to produce compound I". Alternatively, if desired, compound I' can be alkylated to a compound wherein R 1 Compound I is O-C1-C4-alkyl, or acylated to a compound in which R1 O-(C=O)-R 5 Compound I. Suitable alkylation and acylation conditions are described below in the context of Methods A and B.

[0269] The present invention also relates to a method for preparing compound (Ia) and compound (Ib). The reaction of the present invention as described below is carried out in a reaction vessel conventionally used for these reactions, and the reaction is carried out in a continuous, semi-continuous or batch mode. Usually, the specific reaction is carried out under atmospheric pressure. However, the reaction can also be carried out under reduced pressure or elevated pressure.

[0270] More specifically, the present invention relates to a process for preparing a compound of formula (Ia) or a mixture thereof, said process comprising the following steps (i) and optionally steps (ii) to (iv):

[0271] (i) reacting 3-methylbut-3-en-1-ol with furan-2-carbaldehyde in the presence of a Bronsted acid to obtain a crude product mixture containing 1 is a compound of formula (I) as defined herein wherein X is O and R 2 , R 3 , R 4 One and R 1 a compound of formula (I) taken together to represent a double bond; and

[0272] (ii) optionally separating out wherein X is O and R 1 A compound of formula (I) wherein is OH;

[0273] Alternatively, in place of step (ii),

[0274] (iii) wherein X is O and R 2 , R 3 , R 4 One and R 1 The compound of formula (I) together with X being O and R 1 The compound of formula (I) wherein R 2 , R 3 , R 4 One and R 1 Compounds of formula (I) which together represent a double bond are subjected to a hydrogenation reaction;

[0275] Alternatively, instead of steps (ii) and (iii),

[0276] (iv) optionally subjecting the crude product mixture obtained in step (i) to a hydrogenation reaction and optionally isolating the crude product wherein X is O and R 1 A compound of formula (I) wherein:

[0277] This method is also referred to as method A hereinafter.

[0278] Step (ii) obtains 1 is OH compound (Ia), and steps (iii) and (iv) provide a compound in which R 1 is H. Thus, in the first case, method A yields a compound (Ia) in which R 1 is H or OH. However, the compound (Ia) obtained in step (ii) can be further converted into a compound in which R 1 is O-C1-C4-alkyl or O-(C=O)-R 5 The compound (Ia) of

[0279] Accordingly, method A comprises the optional step (v):

[0280] (v) optionally treating the product obtained in step (ii) (i.e., wherein R 1 is OH) or the reaction mixture obtained in step (i) is subjected to an alkylation or acylation reaction (to produce a compound of formula (Ia) wherein R 1 is O-C1-C4-alkyl or O-(C=O)-R 5 Compound (Ia)).

[0281] Usually, one of steps (ii), (iii) or (iv) must be carried out; unless, for example, the compound (Ia) obtained in step (ii) is to be further converted into a compound in which R 1 is O-C1-C4-alkyl or O-(C=O)-R 5 In this case, the reaction mixture as obtained in step (i) can be used for the further transformation without previously isolating the compound in which R 1 is OH, although it is usually advantageous to first isolate the compound in which R 1 Compound (Ia) is OH to reduce the possibility of forming undesirable by-products.

[0282] In step (i) of method A, a crude product mixture is prepared which contains 1 A compound of formula (I) wherein R 1 A compound of formula (Ia) wherein X is O and R 2 , R 3 , R 4 One and R 1A compound of formula (I) which together represents a double bond, i.e. one or more compounds of formula (I-1), (I-2) or (I-3) as defined herein, wherein X is in each case O. The conversion is carried out by reacting isoprenol (3-methylbut-3-en-1-ol) 1 and furfural (furan-2-carbaldehyde) 2 as depicted in the following reaction scheme 2 (compare for example: US 4,962,090, EP 0383446 and L. Liu et al., J. Am. Chem. Soc. 2016, 138, 10822-10825):

[0283] Process 2:

[0284]

[0285] In Scheme 2, formula (II) represents one of the elimination products of formula (I-1), (I-2) or (I-3) as defined herein, wherein X is in each case O, or any mixture of these elimination products. Formula (I.a') represents a compound wherein R 1 A compound of formula (Ia) wherein is OH.

[0286] In step (i), isoprenol and furfural undergo an addition reaction in the presence of a Bronsted acid as a catalyst to produce a 1 is a mixture of a tetrahydropyranol compound of formula (Ia) wherein OH and one or more corresponding elimination products of formula (II). This reaction can be considered to belong to the class of reactions known in the art as Prins reactions.

[0287] Isoprenol and furfural are generally applied in a molar ratio of 0.9: 1 to 1.5: 1, preferably in a molar ratio of 1: 1 to 1.3: 1. It is advantageous to use a slight excess of isoprenol to avoid the formation of acetal as a by-product, which would favor acetal formation if furfural is used in excess.

[0288] 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 strongly acidic cation exchange resins, sulfuric acid, methanesulfonic acid and p-toluenesulfonic acid, especially selected from methanesulfonic acid and strongly acidic cation exchange resins.

[0289] The term "strongly acidic cation exchanger" refers to a cation exchanger having a strongly acidic group. + The strongly acidic groups are usually sulfonic acid groups; they are usually bonded to a polymer matrix which can be, for example, in gel form or macroporous. Preferred are styrene (co)polymers containing sulfonic acid groups, especially styrene-divinylbenzene copolymers containing sulfonic acid groups. Commercial examples of such cation exchangers are (Lanxess), (The Purolite Company), (Dow Chemical Company), (Rohm and Haas Company), (Rohm and Haas Company). Preferred strongly acidic cation exchangers are: K 1221, K 1461, K 2431, K 2620, K 2621, K 2629, K 2649, FPC 22, FPC 23, IR 120, 131. 15. 31. 35. 36. 39. 46. 70. SGC650, C100H, C150H, 50X8, red and NR-50. Specifically, the Branded resins, especially 131. Alternatively, the cation exchanger may be a perfluorinated ion exchange resin, such as DuPont's Brand for sale.

[0290] Unlike acidic cation exchanger resins, Brønsted acids are usually used in catalytic amounts.

[0291] The amount of strongly acidic cation exchanger is not very important, but from the perspective of economy and processing, it is usually used in a catalytic amount. Usually, the strongly acidic cation exchanger is used in an amount of about 5 to about 40 % by weight, preferably in an amount of about 10 to about 40 % by weight, particularly preferably in an amount of about 15 to about 30 % by weight, based on the sum of the weights of 1 and 2 in each case. Here, numerical value refers to a ready-to-use cation exchanger, which is usually pretreated with water, and therefore can comprise a maximum of about 70 % by weight, preferably about 30 to about 70 % by weight, particularly preferably about 40 to about 70 % by weight of water. Especially in the case of discontinuous procedures, it may be superfluous to add water in addition when carrying out the method. The specified strongly acidic cation exchanger can be used independently or in a mixture.

[0292] If an acid other than an acidic cation exchanger is used in the reaction in step (i) of method A, the reaction is generally carried out in a suitable organic solvent which is inert under the reaction conditions of step (i). Suitable solvents are, for example, alkanes such as pentane or hexane, halogenated C1-C4-alkanes such as dichloromethane, chloroform or dichloroethane, cycloalkanes such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, aliphatic ethers such as diethyl ether, diisopropyl ether or methyl-tert-butyl ether, cyclic ethers such as tetrahydrofuran or dioxane, or carboxylic acid esters such as ethyl acetate. The specified solvents can be used alone or in a mixture with one another. Aromatic hydrocarbons are used in particular. If an acidic cation exchanger is used, the reaction can also be carried out in the presence of a solvent which is inert under the reaction conditions. Suitable solvents are those listed above. However, generally, when a strongly acidic cation exchanger is used as a Bronsted acid, the reaction is carried out neat, i.e. without the addition of an organic solvent.

[0293] The reactants can in principle be contacted with one another in any desired order. For example, isoprenol and Bronsted acid (optionally dissolved or dispersed in an inert solvent) can be initially charged and mixed with one another. The resulting mixture is then blended with furfural. Conversely, furfural, optionally dissolved or dispersed in an inert solvent, can be initially charged and blended with a mixture of isoprenol and Bronsted acid. Alternatively, furfural can first be mixed with Bronsted acid and then this mixture can be blended with isoprenol. As a further alternative, all reactants are added to the reaction vessel simultaneously.

[0294] It has been found to be beneficial to initially charge the reaction vessel with a mixture of isoprenol and Bronsted acid, possibly as a dispersion or solution in a solvent, but preferably without solvent, and then add furfural, either used in dissolved form or, preferably, as such.

[0295] Typically, the reaction in step (i) of process A is carried out under temperature control. The reaction is typically carried out in a closed or preferably open reaction vessel with a stirring device. The reaction temperature of the reaction of process A depends on various factors, in particular on the acidity and amount of the Bronsted acid, and can be determined in individual cases by a person skilled in the art, for example by simple preliminary tests. Typically, the conversion of process A is carried out at a temperature of 10 to 150° C., preferably 30 to 120° C., more preferably 40 to 110° C., and in particular 50 to 100° C. In the case where it is desired to obtain a dehydrated compound II having a CC double bond, a higher reaction temperature, for example about 100° C., for example 80 to 120° C. or 90 to 110° C., is advantageous in promoting the elimination and removal of water from the intermediately formed compound I.a'. If a saturated compound I.a' is desired, a reaction temperature below 100° C., such as 30 to 90° C. or 50 to 80° C., is more suitable.

[0296] The work-up of the reaction mixture obtained in step (i) of process A, and wherein R 1 The separation of the mixture of the compound of formula (Ia) wherein R is OH and one or more elimination products of formula (II) is carried out in a conventional manner, for example by aqueous extractive work-up or by removing the solvent, for example under reduced pressure. In general, by adopting such measures or a combination thereof, the compound wherein R is obtained in sufficient purity 1 A mixture of a compound (Ia) in which R is OH and one or more elimination products (II). Therefore, it is usually only desirable to combine the elimination products of formula (II) with the elimination products of formula (II) as described below. 1 An additional purification step, in particular a fine purification step, is only required in the case of the isolation of a compound of formula (Ia) in which R is OH. However, if necessary, the purification step may be carried out by methods commonly used in the art. 1 Further purification of the mixture of compound (Ia) which is OH and one or more elimination products (II).

[0297] Preferably, the reaction mixture obtained in step (i) of process A for workup is diluted with a polar organic solvent, such as ethyl acetate or dichloromethane, which is insoluble or only slightly soluble in water and suitable for dissolving the obtained reaction product. The mixture may then be filtered to remove the cation exchange resin which has been used as Bronsted acid. The obtained product solution is then treated with an alkaline aqueous solution, such as an aqueous sodium bicarbonate solution. After removing the aqueous phase, the organic phase is optionally treated again with the above-mentioned alkaline aqueous solution. Preferably, the organic phase is then washed with an aqueous solution having a neutral or approximately neutral pH value, such as brine. The mixture containing R 1The organic phase of the mixture of compound (Ia) being OH and one or more elimination products (II) is introduced directly or after partial or complete removal of the solvent into the further reaction step. Alternatively, the organic phase is concentrated and the crude product obtained is subsequently retained for use or directly sent to use, for example for further reaction steps, or subjected to further purification steps as described below.

[0298] In the optional step (ii) of method A, the compound obtained in step (i) wherein R 1 The compound (Ia) wherein R is OH and the one or more elimination products (II) are separated from the mixture 1 The separation can be achieved by subjecting the mixture to at least one suitable purification procedure known in the art, such as distillation or chromatography, in particular distillation. In practice, the compound in which R 1 A compound of formula (Ia) wherein is OH.

[0299] In the optional step (iii) of method A, the R 1 A mixture of compound (Ia) wherein X is O and R 2 , R 3 , R 4 One and R 1 The compound of formula (I) together with R 1 The compound (Ia) which is OH is separated. The one or more elimination products (II) are then subjected to a hydrogenation reaction.

[0300] The separation can be achieved using one or more suitable purification procedures known in the art, such as distillation or chromatography, in particular distillation. In practice, the one or more elimination products (II) can be isolated in high purity from the mixture obtained in step (i) of process A by distillation.

[0301] In order to achieve a higher yield of the one or more elimination products (II) after the separation process, it is generally beneficial to increase the yield of the product obtained in step (i) wherein R 1The ratio of the one or more elimination products (II) in the mixture of the compound (Ia) containing OH and the one or more elimination products (II). This can be achieved by applying more intense reaction conditions, such as higher reaction temperature, larger amount of acid or longer reaction time, or by removing water from the reaction equilibrium so that the reaction equilibrium of the conversion in step (i) of method A is moved toward the direction of the elimination product of formula (II). If one or more of these measures are taken, the conversion of step (i) is usually able to completely or nearly completely convert the raw materials isoprenol and furfural into the elimination product of formula (II). Subsequent distillation purification according to step (iii) will then provide the one or more elimination products (II) with good yield and high purity.

[0302] The isolation in step (ii) and the separation in step (iii) can usually be carried out in a single round of purification, in particular in a single round of distillation, to provide a product consisting at least predominantly of R 1 A fraction consisting of compounds of formula (Ia) which are OH and another fraction consisting at least predominantly of the one or more elimination products (II).

[0303] In the hydrogenation reaction of step (iii), as shown in the following Scheme 3, the one or more elimination products (II) obtained in the separation procedure are subjected to a hydrogenation reaction to provide a product wherein R 1 The tetrahydrofuran compound of formula (Ia) (referred to as Ia" in Scheme 3) is H.

[0304] Process 3

[0305]

[0306] Hydrogenation can in principle be achieved by using any hydrogenation method known in the art to be suitable for similar conversions. Preferably, hydrogenation is carried out by using gaseous hydrogen as a reducing agent in the presence of a catalyst that generally comprises at least one transition metal, in particular a metal of 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 in the form of one of their salts, oxides or complexes, or in the form of metals in the catalyst. The preferred metal in this respect is nickel, in particular in the form of Raney nickel. The hydrogenation in step (iii) can be carried out analogously to the transformations described in, for example, JH Tyman et al., Tetrahedron Lett. 1970, 11, 4507; VH Rawal et al., J. Org. Chem. 1993, 58, 7718; BMTrost et al., J. Am. Chem. Soc. 2006, 128, 6745; L. Coulombel et al., Eur. J. Org. Chem. 2009, 33, 5788; and P L Alsters et al., Org. Process Res. Dev. 2010, 14, 259.

[0307] The hydrogenation in step (iii) of process A can be carried out without solvent, but is preferably carried out in the presence of a solvent which is inert under the hydrogenation conditions, such as an especially protic organic solvent, preferably selected from C1-C6-alkanols, in particular from methanol, ethanol and isopropanol.

[0308] The hydrogenation is generally carried out at a hydrogen pressure of 1 to 2 bar, preferably 1 to 1.5 bar, in particular 1 to 1.2 bar. The temperature is generally in the range of 10 to 50°C, preferably 20 to 40°C, for example 20 to 30°C or 20 to 25°C.

[0309] The work-up of the reaction mixture obtained in step (iii) of process A and wherein R 1 The isolation of the tetrahydrofuran compound of formula (Ia) which is H is carried out in a customary manner, for example by filtration and removal of the solvent, for example under reduced pressure. Typically, R is then obtained in sufficient purity. 1 The product of formula (Ia) is H, and additional purification steps such as chromatography or distillation are usually not necessary, but if extremely pure R is required 1 The product of formula (Ia) where H is H may also be used.

[0310] In the optional step (iv) of method A, as shown in Scheme 3 above, the R 1 A mixture of compound (Ia) wherein R is OH and one or more elimination products (II) is subjected to a hydrogenation reaction to provide R 1 is a tetrahydrofuran compound of formula (Ia) wherein H is

[0311] The hydrogenation reaction in step (iv) is carried out analogously to that described above for process A, step (iii).

[0312] In order to achieve R 1 In order to obtain a higher yield of the tetrahydrofuran compound of formula (Ia) wherein R is H, in step (iv) of process A, it is generally beneficial to increase the yield of the tetrahydrofuran compound of formula (Ia) wherein R is H. 1 The ratio of the elimination product (II) in the mixture of the compound (Ia) of OH and the one or more elimination products (II). This can be achieved by applying one or more of the above-mentioned measures to shift the reaction equilibrium of the conversion in step (i) of method A towards the direction of the elimination product of formula (II).

[0313] In addition, the R 1 The tetrahydrofuranol compound of formula (Ia) wherein R is OH is subjected to an alkylation reaction to prepare 1 The compound of formula (Ia) is O-C1-C4-alkyl.

[0314] The alkylation reaction is carried out under conventional alkylation reaction conditions known in the art. Preferably, by using an alkylating agent R 6 -Y (where R 6 is C1-C4-alkyl and Y represents a leaving group selected from halogen such as Cl, Br, I, and sulfonate, toluenesulfonate, mesylate, trifluoromethanesulfonate or perfluorobutanesulfonate) is usually reacted with R in the presence of a base. 1 Compound (Ia) is alkylated to prepare R 1 Compound (Ia) is O-C1-C4-alkyl.

[0315] Suitable bases are generally selected from inorganic bases and organic bases.

[0316] Suitable inorganic bases which can be used for 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.

[0317] Suitable organic bases which can be used for such alkylation reactions are, for example, tertiary amines, such as trimethylamine, triethylamine, tripropylamine, ethyldiisopropylamine, etc., or basic N-heterocycles, such as morpholine, pyridine, lutidine, DMAP, DABCO, DBU or DBN.

[0318] Work-up of the reaction mixture obtained in the alkylation reaction, and R 1The isolation of the product of formula (Ia) which is O-C1-C4-alkyl is carried out in a conventional manner, for example by aqueous extraction work-up or by removal of the solvent, for example under reduced pressure. In general, by adopting such measures or a combination thereof, the desired product is obtained in sufficient purity. However, if extremely pure R is required 1 Compounds of the formula (Ia) which are O-C1-C4-alkyl can be subjected to additional purification steps, such as chromatography or distillation.

[0319] Alternatively, the product obtained in step (i) or step (ii) of method A wherein R 1 A tetrahydropyranol compound of formula (Ia) wherein R is OH is subjected to an acylation reaction to prepare 1 O-(C=O)-R 5 A compound of formula (Ia).

[0320] Usually, by making R 1 The compound (Ia) is OH and the carboxylic acid R 5 -COOH (where R 5 has the meaning defined herein) or its anhydride, or a carboxylic acid R 5 -COOH reacts with a mixture of its anhydrides to efficiently prepare R 1 O-(C=O)-R 5 The reaction is usually carried out in the presence of an esterification catalyst or a base.

[0321] Suitable esterification catalysts which can be used for this reaction are well known in the art. Suitable esterification catalysts are, for example, metal-based catalysts, such as iron, cadmium, cobalt, lead, zinc, antimony, magnesium, titanium and tin catalysts in the form of metals, metal oxides or metal salts such as metal alkoxides, inorganic acids such as sulfuric acid, hydrochloric acid or phosphoric acid, or organic sulfonic acids such as methanesulfonic acid or p-toluenesulfonic acid.

[0322] Suitable bases are, for example, organic bases as specified above, such as, in particular, pyridine, lutidine or DMAP, especially DMAP.

[0323] Alternatively, by making R 1 The compound (Ia) is OH and the formula R 5 -(C=O)Y' acyl halide (where R 5 has one of the meanings defined herein and Y' is a halogen such as Cl, Br or I) in the presence of an organic base, preferably one of the organic bases defined above, to prepare R 1 O-(C=O)-R 5 An ester of formula (Ia).

[0324] Preferably, by making R 1 The compound (Ia) is OH and the carboxylic acid R5 -COOH anhydride reacts in the presence of an organic base to prepare R 1 O-(C=O)-R 5 An ester of formula (Ia).

[0325] For the preparation of R as outlined above 1 O-(C=O)-R 5 The respective reaction conditions for esters of formula (Ia) are well known in the art.

[0326] The work-up of the reaction mixture obtained in the acylation reaction, and R 1 O-(C=O)-R 5 The isolation of the product of formula (Ia) is carried out in a conventional manner, for example by aqueous extraction work-up or by removing the solvent, for example under reduced pressure. Usually, by adopting such measures or a combination thereof, the desired product is obtained in sufficient purity. However, if extremely pure R is required 1 O-(C=O)-R 5 The compound of formula (Ia) may be subjected to additional purification steps, such as chromatography or distillation.

[0327] The present invention further relates to a process for preparing one of the compounds of formula (Ib) as defined above or a mixture thereof, said process comprising the following step (i') and optionally steps (ii') to (v'):

[0328] (i') reacting 3-methylbut-3-en-1-ol with thiophene-2-carboxaldehyde in the presence of a Bronsted acid to obtain a crude product mixture containing 1 A compound of formula (Ib) wherein R 2 , R 3 , R 4 One and R 1 A compound of formula (Ib) together representing a double bond,

[0329] (ii') optionally separating the R 1 A compound of formula (Ib) wherein is OH;

[0330] Alternatively, instead of step (ii'),

[0331] (iii') optionally wherein R 2 , R 3 , R 4 One and R 1 The compound of formula (Ib) together with R 1 The compound of formula (Ib) wherein R is OH is isolated, and if necessary, 2 , R 3 , R4 One and R 1 Compounds of formula (Ib) which together represent a double bond are subjected to a hydrogenation reaction;

[0332] Alternatively, instead of steps (ii') and (iii'),

[0333] (iv') optionally subjecting the crude product mixture obtained in step (i) to a hydrogenation reaction and optionally separating the R 1 A compound of formula (Ib) wherein

[0334] Alternatively, as an alternative or in addition to steps (iii') and (iv'),

[0335] (v') Optional pair where R 1 The compound of formula (Ib) which is OH is subjected to an alkylation or acylation reaction.

[0336] This method is also referred to herein as Method B.

[0337] Step (ii') yields 1 is OH compound (Ib), step (iii') obtains a compound wherein R 2 , R 3 , R 4 One and R 1 Compounds (Ib) which together represent a double bond (if no hydrogenation reaction is carried out) or, if these compounds are hydrogenated, give compounds in which R 1 is hydrogen compound (Ib), and step (iv') yields a compound wherein R 1 is H. Step (v') provides a compound (Ib) wherein R 1 is O-C1-C4-alkyl or O-(C=O)-R 5 Compound (Ib).

[0338] Usually, one of steps (ii'), (iii') or (iv') must be carried out; unless, for example, the compound (Ib) obtained in step (ii) is to be further converted in step (v') into a compound in which R 1 is O-C1-C4-alkyl or O-(C=O)-R 5 In this case, the reaction mixture as obtained in step (i) can be used for the further transformation in step (v') without previously isolating in step (ii') the compound in which R 1 is OH, although it is often advantageous to first isolate in step (ii') the compound (Ib) in which R 1 Compound (Ib) is OH to reduce the possibility of forming undesirable by-products in step (v').

[0339] Steps (i') to (iv') of method B correspond to steps (i) to (iv) of method A of the present invention and can be carried out similarly to the procedures described above for steps (i) to (iv), except that thiophene-2-carboxaldehyde is used instead of furfural in step (i') and the hydrogenation reaction is omitted in step (iii'), so as to obtain 2 , R 3 , R 4 One and R 1 In addition, the alkylation and acylation reactions according to step (v') of method B correspond to those described above for R 1 The procedure for the alkylation or acylation of the tetrahydropyranol compound of formula (Ia) which is OH can be carried out in an analogous manner.

[0340] Compounds (I) other than compounds (Ia) and (Ib) (e.g., wherein X is O and R 2 , R 3 , R 4 One and R 1 For example, compounds (I) in which X is O and R 2 , R 3 , R 4 One and R 1 Compound (I) wherein X is O and R 2 , R 3 , R 4 One and R 1 Together they represent a compound (I) having a double bond.

[0341] The following examples are provided to further illustrate the present invention. Example

[0342] Preparation Example

[0343] abbreviation:

[0344] DMAP:4-(dimethylamino)-pyridine

[0345] EA: Ethyl acetate

[0346] RT: Room temperature

[0347] THF: Tetrahydrofuran

[0348] MTBE: Methyl-tert-butyl ether

[0349] analyze:

[0350] The purity of the product was determined by gas chromatography based on area %:

[0351] GC column: DB-WAX (30 m (length), 0.25 mm (ID), 0.25 μm (film));

[0352] Temperature program: 5 min at 50°C, 6°C / min from 50°C to 230°C, 10 min at 230°C. Injector temperature 200°C; detector temperature 230°C. Flow rate: 1.4 ml / min

[0353] pass 13 C NMR identified the product.

[0354] 1a) Preparation of 2-(furan-2-yl)-4-methyl-tetrahydropyran-4-ol (R 1 =OH) and the corresponding three elimination products with an exocyclic or endocyclic double bond (X = O and R 2 , R 3 or R 4 With R 1 together represent a double bond)

[0355] To isoprenol (3-methylbut-3-en-1-ol) (40 g, 0.464 mol) and 20 g of a strongly acidic cation exchanger To a mixture of 131 (wet; from Rohm & Haas; washed with water, then with methanol and then with water before use) was added furfural (37.9 g, 0.395 mol) slowly under stirring at room temperature. The exothermic reaction was continued at a temperature of 70° C. for 3 hours. Thereafter the reaction mixture was set to RT and the cation exchanger was filtered off. The filtrate was mixed with 100 ml EA and 100 ml water. The organic phase was separated and washed with saturated aqueous NaHCO3 solution and then with brine. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 47.9 g of a crude product were obtained, which, according to GC analysis (area %), contained approximately 71.84% of 2-(furan-2-yl)-4-methyl-tetrahydropyran-4-ol and 19.95% of the elimination products 2-(furan-2-yl)-4-methylene-tetrahydropyran, 2-(furan-2-yl)-4-methyl-5,6-dihydro-2H-pyran and 2-(furan-2-yl)-4-methyl-5,6-dihydro-2H-pyran. The crude product was subjected to distillation separation to produce two main fractions.

[0356] The first fraction of the distillation proved to be a mixture of three elimination products with a purity of 95.3% (GC area %) and a molar ratio of compounds I-1:I-2:I-3 of 1:65.5:33.5, wherein X was O in each case.

[0357] Dihydropyran analogs:

[0358] 13 C NMR (125MHz, CDCl3): δ=22.97,33.26,65.79,68.89,106.77,110.08,119.64,131.19,142.21,154.41

[0359] Methylene Analogs:

[0360] 13 C NMR (125MHz, CDCl3): δ=34.82,38.64,68.47,73.53,106.78,109.58,110.06,142.29,143.28,154.19

[0361] The second fraction was confirmed to be 2-(furan-2-yl)-4-methyl-tetrahydropyran-4-ol with a purity of 97.7% (GC area %) and a 3:1 ratio of E and Z isomers as determined by NMR.

[0362] E Isomer:

[0363] 13 C NMR (125MHz, CDCl3): δ=22.33,26.11,35.54,39.81,63.77,68.28,78.79,106.74,110.11,142.29,154.13,170.32

[0364] Z Isomer:

[0365] 13 C NMR (125MHz, CDCl3): δ=21.57,22.41,37.26,40.66,64.72,69.93,79.33,106.70,110.14,142.31,153.83,170.24

[0366] The reaction was repeated and 398.7 g of the crude product were subjected to rectification using a 60 cm column with a diameter of 4 cm. 59 cm of the column was filled with column packing (DN30 A3-1000 2.4610 8 27x50 mm). Several fractions were separated, fraction 4 being the isomer I-2 (X=O) with a purity of 97.3%.

[0367] 1b) Preparation of a mixture of 2-(furan-2-yl)-dihydropyran and 2-(furan-2-yl)-4-methylene-tetrahydropyran having an endocyclic or exocyclic double bond (= elimination product of 2-(furan-2-yl)-4-methyl-tetrahydropyran-4-ol; a mixture of compounds I-1, I-2 and I-3 wherein X=O and R 2 , R 3 or R 4 With R 1 A mixture of compounds of formula (I)

[0368] A mixture of isoprenol (21.50 g, 0.249 mol) and furfural (20 g, 0.208 mol) in 200 ml of toluene was stirred at 20°C. At this temperature, 2 drops of methanesulfonic acid were added to the reaction mixture (slightly exothermic). The mixture was stirred at reflux for 5 hours while distilling water during the reaction. Thereafter, the reaction mixture was set to RT. 100 ml of water was added to the mixture and the organic phase was washed with 5% NaHCO3 solution and water. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 30.3 g of a crude product were obtained, which, according to GC analysis (area %), contained about 6% of 2-(furan-2-yl)-4-methyl-tetrahydropyran-4-ol and 80.7% of the elimination products 2-(furan-2-yl)-4-methylene-tetrahydropyran, 2-(furan-2-yl)-4-methyl-5,6-dihydro-2H-pyran and 2-(furan-2-yl)-4-methyl-5,6-dihydro-2H-pyran. The crude product was subjected to distillation separation to produce a main fraction, which was confirmed to be a mixture of three elimination products, with a purity of 97.8% (GC area %) and a molar ratio of compounds I-1:I-2:I-3 of 1:19.5:79.5, wherein X is O in each case.

[0369] The reaction was repeated and 59.9 g of the crude product were subjected to rectification using a 21 cm column equipped with column packing (DN30 A3-1000 2.4610 8 27x50 mm). Several fractions were isolated, fraction 3 containing 7% 1-2 and 92% 1-3, wherein X was O in each case.

[0370] 1c) Preparation of 2-(2-furan-2-yl)-4-methyl-tetrahydropyran (R 1 is a compound of formula (Ia) wherein

[0371] 15 g of three elimination products I-1, I-2 and I-3 (X=O and R 2 , R 3 or R 4 With R 1A mixture of 2-(2-furanyl)-4-methyl-tetrahydropyran (2-(2-furanyl)-4-methyl) ...

[0372] Z Isomer:

[0373] 13 C NMR (125MHz, CDCl3): δ=22.25,30.18,34.25,38.13,68.27,72.81,106.02,110.01,141.83,155.13

[0374] E Isomer:

[0375] 13 C NMR (125MHz, CDCl3): δ=20.19,25.22,33.00,35.26,62.60,68.27,107.18,109.99,141.83,154.84

[0376] 1d) Preparation of 2-(furan-2-yl)-4-methyl-tetrahydropyran-4-yl-acetic acid ester (R 1 is a compound of formula (Ia) wherein O-(C=O)-CH3)

[0377] DMAP (0.2 g, 1.64 mmol) was added to a solution of 2-(furan-2-yl)-4-methyl-tetrahydropyran-4-ol (10 g, 0.055 mol) in 50 ml of THF at room temperature. The resulting mixture was refluxed at 53 ° C, while acetic anhydride (7 g, 1.25 eq.) was slowly added at this temperature. After 6 hours, about 85% conversion was observed by GC. The reaction was cooled to RT and slowly quenched with 50 ml of water. Thereafter, 50 ml of EA was added. The organic phase was separated and washed with saturated NaHCO3 aqueous solution and brine. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 6.9 g of crude product was obtained, which contained about 81.5% of the title compound according to GC analysis (area %). Purification by column chromatography provided a purity of 99% (GC area %) of the title compound as a mixture of its E and Z isomers. NMR analysis revealed an E / Z isomer ratio of 7:3.

[0378] E Isomer:

[0379] 13 C NMR (125MHz, CDCl3): δ=31.59,38.14,42.03,63.94,67.52,68.44,106.65,110.03,142.16,154.61

[0380] Z Isomer:

[0381] 13 C NMR (125MHz, CDCl3): δ=25.19,40.05,43.58,65.59,68.55,70.66,106.75,110.13,142.25,154.05

[0382] 1e) Preparation of 2-(2-furan-2-yl)-4-methoxy-4-methyl-tetrahydropyran (R 1 is a compound of formula (Ia) wherein OCH3

[0383] To a dispersion of sodium hydride (1.3 eq) in 75 ml of THF was slowly added 10 g of 2-(furan-2-yl)-4-methyl-tetrahydropyran-4-ol (R 1 =OH of the formula (Ia) compound) in 30 ml of THF. The mixture was stirred at 0 ° C for 30 minutes. Then 1.3 equivalents of iodomethane were 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 0.25 equivalents of NaH were added again, followed by 0.25 equivalents of iodomethane. Then the mixture was stirred at 40 ° C for 17 hours. The reaction was slowly quenched with 50 ml of water. The organic phase was extracted three times with 50 ml of MTBE. The organic extracts were combined and washed with 50 ml of NH3 solution and 50 ml of brine. The organic extracts were combined and dried with sodium sulfate. After evaporating the solvent under reduced pressure, 9.6 grams of crude product were obtained, which contained 95% of the desired methyl ether according to GC (area %). The crude product was subjected to distillation separation to produce the main fraction, which was confirmed to be the desired 2-(2-furan-2-yl)-4-methoxy-4-methyl-tetrahydropyran with a purity of 99% (GC area %). NMR analysis indicated a 7:3 E / Z mixture.

[0384] E Isomer:

[0385] 13 C NMR (125MHz, CDCl3): δ=24.84,34.92,39.22,48.69,63.77,68.12,71.18,106.44,110.01,142.13,154.84

[0386] Z Isomer:

[0387] 13 C NMR (125MHz, CDCl3): δ=20.26,36.59,40.33,48.20,65.43,70.42,72.48,106.51,110.11,142.20,154.35

[0388] 1f) Preparation of 2-(thiophen-2-yl)-4-methyl-tetrahydropyran-4-ol (R 1 is OH and R 2 , R 3 and R 4 Each of the compounds of formula (Ib) is H

[0389] To isoprenol (20 g, 0.232 mol) and 10 g of a strongly acidic cation exchanger To a mixture of 131 (wet; from Rohm & Haas), thiophene-2-carboxaldehyde (22.13 g, 0.197 mol) was slowly added at room temperature under stirring. The exothermic reaction was continued at a temperature of 70° C. for 3 hours. Thereafter, the reaction mixture was set to RT and the cation exchanger was filtered off. The filtrate was mixed with 100 ml of EA and 100 ml of water. 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, 28.5 g of a crude product were obtained, which, according to GC analysis (area %), contained approximately 67.45% of 2-(thiophen-2-yl)-4-methyl-tetrahydropyran-4-ol and 14.68% of the elimination products 2-(thiophen-2-yl)-4-methylene-tetrahydropyran, 2-(thiophen-2-yl)-4-methyl-5,6-dihydro-2H-pyran and 2-(thiophen-2-yl)-4-methyl-5,6-dihydro-2H-pyran. The crude product was subjected to distillation separation to produce two main fractions.

[0390] The major fraction was 2-(thiophen-2-yl)-4-methyl-tetrahydropyran-4-ol with a purity of 98.2% (GC area %) and a ratio of E to Z isomers of 55:45 as determined by NMR.

[0391] E Isomer:

[0392] 13 C NMR (125MHz, CDCl3): δ=31.55,38.14,46.23,64.14,67.86,71.07,123.57,124.47,126.38,145.80

[0393] Z Isomer:

[0394] 13 C NMR (125MHz, CDCl3): δ=25.19,40.01,47.73,65.79,68.76,73.22,123.74,124.78,126.38,145.09

[0395] 1g) Preparation of a mixture of 2-(thiophen-2-yl)-dihydropyran and 2-(thiophen-2-yl)-4-methylene-tetrahydropyran having an endocyclic or exocyclic double bond (= elimination product of 2-(thiophen-2-yl)-4-methyl-tetrahydropyran-4-ol; mixture of compounds I-1, I-2 and I-3 with X=S=R 2 , R 3 or R 4 With R 1 A mixture of compounds of formula (Ib) which together represent a double bond

[0396] To a solution of the distillate from Example 1f) (5.5 g, 0.027 mol) in 35 ml of toluene was slowly added 0.8 g of NaHSO4 (0.007 mol) at room temperature. The reaction was stirred at 110° C. (reflux) for 3 hours. Thereafter, a 37% conversion of 2-(thiophene-2-yl)-4-methyl-tetrahydropyran-4-ol was observed and the reaction was stopped. The mixture was cooled to RT and the NaHSO4 was filtered off. 50 ml of water were added to the filtrate. The organic phase was separated and washed with water and brine. The organic extracts were combined and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 2.4 g of crude product were obtained, which, according to GC analysis (area %), contained approximately 61% of 2-(thiophen-2-yl)-4-methyl-tetrahydropyran-4-ol and 36% of the elimination products 2-(thiophen-2-yl)-4-methylene-tetrahydropyran, 2-(thiophen-2-yl)-4-methyl-5,6-dihydro-2H-pyran and 2-(thiophen-2-yl)-4-methyl-5,6-dihydro-2H-pyran. Purification by column chromatography afforded the title compound with a purity of 98.8% (GC area %) and a molar ratio of compounds I-1:I-2:I-3 of 1:39:60, wherein X is S in each case.

[0397] Dihydropyran analogs:

[0398] 13 C NMR (125MHz, CDCl3): δ=22.91,37.33,66.15,71.55,119.72,123.77,124.68,126.43,131.37,145.59

[0399] Methylene Analogs:

[0400] 13 C NMR (125MHz, CDCl3): δ=34.77,42.78,68.89,76.37,109.46,123.64,124.69,126.45,143.53,145.37

[0401] 1h) Preparation of 2-(2-furan-2-yl)-4-ethoxy-4-methyl-tetrahydropyran (R 1 is a compound of formula (Ia) wherein OCH2CH3

[0402] To a dispersion of sodium hydride (1.3 eq) in 70 ml of toluene was slowly added 12 g of 2-(furan-2-yl)-4-methyl-tetrahydropyran-4-ol (R 1 =OH) in 20 ml of toluene. The mixture was stirred at 0°C for 30 minutes. The reaction was heated to 87°C for 2 hours and 0.7 equivalents of diethyl sulfate were slowly added at this temperature. After the addition, the mixture was stirred at 87°C for 3 hours. The reaction was slowly quenched with 50 ml of water, and then the mixture was stirred at room temperature for 48 hours. The organic phase was separated and dried over sodium sulfate. After evaporation of the solvent under reduced pressure, 11.2 grams of crude product were obtained, which contained 90% of the desired ethyl ether according to GC (area %), with a Z / E ratio of 30:60. Purification by column chromatography produced two major fractions, which were confirmed to be the desired 2-(2-furan-2-yl)-4-ethoxy-4-methyl-tetrahydropyran. NMR analysis showed that the first fraction was the E isomer (95% purity [GC area %]) and the second fraction was a Z / E mixture of 85:15 (97% purity [GC area %]).

[0403] E Isomer:

[0404] 13 C NMR (125MHz, CDCl3): δ=16.01,25.57,35.45,39.66,56.06,63.87,68.18,71.00,106.39,110.01,142.10,154.96

[0405] Z Isomer:

[0406] 13 C NMR (125MHz, CDCl3): δ=16.13,20.99,37.10,40.85,55.52,65.42,70.38,72.29,106.48,110.10,142.17,155.46

[0407] 2. Olfactory test

[0408] In order to test the quality and intensity of the odor of the compound (I) of the present invention, an aroma paper test was performed.

[0409] For this purpose, a test strip of absorbent paper is dipped into a solution containing a 1 to 10% by weight solution of the test compound (I) in ethanol. After evaporation of the solvent (approximately 30 seconds), the aroma impression is assessed olfactorily by a trained perfumer.

[0410] The results of the aroma tests are summarized in Table 1.

[0411] Table 1: Results of aroma test

[0412]

[0413]

[0414]

Claims

1. Use of the compound of general formula (I) or a mixture of its stereoisomers as an aromatic chemical: in X is O or S; R 1 is hydrogen, OH or O-C1-C4-alkyl; R 2 , R 3 , R 4 It is hydrogen; or R 3 With R 1 together they represent a double bond; or Use of a mixture of at least two compounds I-1, I-2 and I-3 or a mixture of their stereoisomers as an aroma chemical, wherein compound I-1 is a compound wherein R 2 With R 1 The compound of formula (I) together represents a double bond, compound I-2 is wherein R 3 With R 1 together represent a double bond, and compound I-3 is a compound of formula (I) wherein R 4 With R 1 a compound of formula (I) which together represent a double bond, wherein X in all compounds I-1, I-2 and I-3 contained in the mixture has the same meaning, The uses described herein do not include use in diagnosis and treatment of diseases.

2. The use according to claim 1, wherein the mixture of at least two compounds I-1, I-2 and I-3 is a mixture containing compound I-2 and one or both of compounds I-1 and I-3, or a mixture containing compounds I-1 and I-2 and optionally also containing compound I-3, or a mixture containing compounds I-2 and I-3 and optionally also containing compound I-1, wherein X in all compounds I-1, I-2 and I-3 contained in the mixture has the same meaning.

3. The use according to claim 2, wherein the mixture contains compounds I-2 and I-3 and optionally also compound I-1, wherein compound I-1 is contained in an amount of 0 to 10% by weight, compound I-2 is contained in an amount of 1 to 80% by weight, and compound I-3 is contained in an amount of 15 to 99% by weight, relative to the total weight of compounds I-1, I-2 and I-3.

4. The use according to claim 3, wherein the mixture contains compounds I-1, I-2 and I-3, wherein compound I-1 is contained in an amount of 0.1 to 10 weight %, compound I-2 is contained in an amount of 1 to 79.9 weight %, and compound I-3 is contained in an amount of 15 to 99 weight % relative to the total weight of compounds I-1, I-2 and I-3.

5. The use according to claim 4, wherein the compound I-1 is contained in an amount of 0.5 to 1.5 wt. %, the compound I-2 is contained in an amount of 15 to 73.5 wt. %, and the compound I-3 is contained in an amount of 25 to 84.5 wt. %, relative to the total weight of the compounds I-1, I-2 and I-3.

6. The use according to claim 1, wherein in formula (I), R 1 It's hydrogen.

7. The use according to claim 1, wherein in formula (I), R 1 It's OH.

8. The use according to claim 1, wherein in formula (I), R 1 It is O-C1-C4-alkyl.

9. The use according to claim 8, wherein in formula (I), R 1 It is methoxy or ethoxy.

10. The use according to claim 9, wherein in formula (I), R 1 It's a methoxy group.

11. Use according to any one of the preceding claims, wherein X is O.

12. The use according to any one of claims 1 to 10, wherein X is S.

13. The use according to any one of the preceding claims 1 to 10 for presenting an olfactory impression.

14. The use according to claim 13 as a fragrance.

15. Use of a compound of formula (I), a mixture of its stereoisomers or a mixture of different compounds (I) as claimed in any one of claims 1 to 12 for modifying the aroma profile of a perfuming ready-to-use composition, excluding diagnostic and therapeutic uses for diseases.

16. Use according to any of the preceding claims for the preparation of a composition selected from perfume compositions, hygiene articles, compositions for diffusers, pharmaceutical compositions and crop protection compositions.

17. Use according to any one of the preceding claims for the preparation of a composition selected from body care compositions, oral dental hygiene products and cleaning compositions.

18. Use according to claim 17, wherein the cleaning composition is a fabric detergent composition.

19. A composition comprising at least one compound of formula (I), a mixture thereof or a mixture of its stereoisomers as claimed in any one of claims 1 to 12, and at least one additional compound selected from aroma chemicals and non-aromatic chemical carriers different from compound (I), wherein the non-aromatic chemical carrier is selected from surfactants, emollients and solvents, wherein the solvent is selected from ethanol, isopropanol, propylene glycol, dipropylene glycol, 1,2-butylene glycol, diethylene glycol monoethyl ether, glycerol, diethyl phthalate, isopropyl myristate, triethyl citrate and benzyl benzoate.

20. The composition according to claim 19, selected from perfume compositions, hygiene products, compositions for diffusers, pharmaceutical compositions and crop protection compositions.

21. A composition according to the preceding claim 19 for use in the preparation of a composition selected from the group consisting of body care compositions, oral dental hygiene products and cleaning compositions.

22. A composition according to claim 21 wherein the cleaning composition is a fabric detergent composition.

23. A compound of formula (Ia), a mixture thereof, or a mixture of its stereoisomers in R 1 is hydrogen, OH or O-C1-C4-alkyl.

24. A compound according to claim 23, wherein R 1 is selected from hydrogen, OH, methoxy, ethoxy and acetoxy.

25. A compound according to claim 23, wherein R 1 is OH or O-C1-C4-alkyl.

26. A compound according to claim 25, wherein R 1 It is OH, methoxy or ethoxy.

27. A compound according to claim 26, wherein R 1 It is OH or methoxy.

28. A compound of formula (Ib) or a mixture of its stereoisomers in R 1 Yes OH, R 2 , R 3 , R 4 It's hydrogen.

29. A mixture of at least two different compounds of formula (I) as claimed in claim 1, wherein X in formula (I) is S; wherein the mixture is a mixture of at least two compounds I-1, I-2 and I-3, wherein in compound I-1 R 2 With R 1 Together they represent a double bond. In compound I-2, R 3 With R 1 together represent a double bond, and in compound I-3 R 4 With R 1 together represent a double bond.

30. A mixture according to claim 29, wherein the mixture is a mixture containing compound 1-2 and one or both of compounds 1-1 and 1-3; or a mixture containing compounds 1-1 and 1-2 and optionally also containing compound 1-3; or a mixture containing compounds 1-2 and 1-3 and optionally also containing compound 1-1; or a mixture containing compounds 1-1, 1-2 and 1-3.

31. The mixture according to claim 30, wherein the mixture is a mixture containing compounds I-1 and I-2.

32. A mixture of at least two different compounds of formula (I) as described in claim 1, wherein the mixture contains compounds I-2 and I-3 and optionally also compound I-1, wherein compound I-1 is contained in an amount of 0 to 10 weight-%, compound I-2 is contained in an amount of 1 to 80 weight-%, and compound I-3 is contained in an amount of 15 to 99 weight-%, relative to the total weight of compounds I-1, I-2 and I-3, wherein X in all compounds I-1, I-2 and I-3 contained in the mixture has the same meaning.

33. A mixture according to claim 32, wherein the mixture contains compounds I-1, I-2 and I-3, wherein compound I-1 is contained in an amount of 0.1 to 10 weight %, compound I-2 is contained in an amount of 1 to 79.9 weight %, and compound I-3 is contained in an amount of 15 to 99 weight % relative to the total weight of compounds I-1, I-2 and I-3.

34. A mixture according to claim 33, wherein Compound I-1 is contained in an amount of 0.5 to 1.5 wt %, compound I-2 is contained in an amount of 15 to 73.5 wt %, and compound I-3 is contained in an amount of 25 to 84.5 wt % relative to the total weight of compounds I-1, I-2 and I-3.

35. A process for preparing a compound of formula (Ia) according to any one of claims 23 to 27 or a mixture of different compounds (Ia), the process comprising: In order to prepare R 1 is a compound of formula (Ia) or a mixture thereof wherein (i) reacting 3-methylbut-3-en-1-ol with furan-2-carbaldehyde in the presence of a Bronsted acid to obtain a crude product mixture containing 1 A compound of formula (I) as claimed in claim 1 wherein X is O and R 2 , R 3 , R 4 One and R 1 a compound of formula (I) taken together to represent a double bond; and (ii) optionally separating out wherein X is O and R 1 A compound of formula (I) wherein is OH; Alternatively, in place of step (ii), (iii) wherein X is O and R 2 , R 3 , R 4 One and R 1 The compound of formula (I) together with X being O and R 1 The compound of formula (I) wherein R 2 , R 3 , R 4 One and R 1 Compounds of formula (I) which together represent a double bond are subjected to a hydrogenation reaction; Alternatively, instead of steps (ii) and (iii), (iv) optionally subjecting the crude product mixture obtained in step (i) to a hydrogenation reaction and optionally isolating the crude product wherein X is O and R 1 A compound of formula (I) wherein H is and in order to prepare 1 A compound of formula (Ia) which is O-C1-C4-alkyl: (v) For which R 1 The compound of formula (Ia) which is OH is subjected to an alkylation reaction.

36. A process for preparing a compound of formula (Ib) or a mixture of different compounds of formula (Ib) according to claim 28, the process comprising (i') reacting 3-methylbut-3-en-1-ol with thiophene-2-carbaldehyde in the presence of a Bronsted acid to obtain a crude product mixture containing 1 A compound of formula (Ib) wherein R 2 , R 3 , R 4 One and R 1 A compound of formula (Ib) together representing a double bond, (ii') optionally separating the R 1 A compound of formula (Ib) wherein is OH; Alternatively, instead of step (ii'), (iii') optionally wherein R 2 , R 3 , R 4 One and R 1 The compound of formula (Ib) together with R 1 The compound of formula (Ib) which is OH is isolated.

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