WO2019037862A1 - ORGANOSCHWEFELVERBINDUNGEN AS RICH AND FLAVORINGS - Google Patents

Abstract

The invention relates to organosulfur compounds which can be obtained from rose oxide, processes for the production of organosulfur compounds and their use as perfuming agents, flavoring agents or ingredients in perfume mixtures, as well as products derived therefrom, in particular perfume oil compositions, detergents and shower gels.

Description

 Organosulfur compounds as fragrances and flavorings

[1] The invention relates to novel organosulfur compounds of the formula (I)

und deren Herstellung. Die nach der Erfindung beanspruchten Verbindungen der Formel (I) liegen als verschiedene erfindungsgemäße Isomere, Diastereomere und Enantiomere vor. Weiterhin betrifft die Erfindung die Herstellung der Verbindungen und Gemische, sowie deren Verwendung als Riech- und Geschmackstoffe oder Konsumgüter enthaltend diese Mischungen.

and their production. The compounds of the formula (I) claimed according to the invention are present as various isomers, diastereomers and enantiomers according to the invention. Furthermore, the invention relates to the preparation of the compounds and mixtures, and their use as fragrances and flavorings or consumer goods containing these mixtures.

On the part of the perfumery or flavor industry, there is an increasing demand for new fragrances and flavors that allow an expansion of the partuman or the flavoristic range. The introduction of such new fragrances and flavorings becomes all the more valuable as they bring added value from the sustainability point of view.

[3] High impact materials are characterized by a strong odor intensity combined with a very low concentration. Due to the low dosage in perfume oils and thus low pollution of the wastewater, they are classified as relatively environmentally friendly fragrances. Similarly, producing smaller quantities of a chemical also means lower energy and reagent consumption. In addition, transport volumes are reduced so that the carbon footprint is low compared to conventional fragrances. Finally, low dosages of chemical fragrances and flavorings improve the human health burden. [4] Organo-sulfur compounds as exceptionally strong fragrances, so-called high impact materials, are known in principle. Examples of these are the compounds shown below, thiocineol (1), tropicol (2), cassix 150 (3), passiflorane (4), oxanthia (5) and thiohexanol (6), which have outstanding fruity odor notes (Arctander "Perfume and Flavor Chemicals ( Aroma Chemicals) ", 2008, Vol. 1).

 Passiflorane 4 Oxanthia 5 Thiohexanol 6

The invention is based on the general object to provide new high impact materials that can be used in small doses as fragrances and flavorings.

[6] Another object of the invention relates to the preparation of such novel high impact materials in any form of their isomers, diastereomers and enantiomers, and mixtures thereof.

An additional object is the reduction or masking of an unpleasant odor or taste and / or enhancing positive odor or taste impressions, especially the strengthening of floral and fruity odor or taste impressions by new inventive compounds or mixtures thereof. [8] Another object is to provide new compounds for use as fragrances and flavors, preferred blends, and consumer products containing these blends and their preparation.

[9] These objects are achieved by the feature combinations defined in the main claims. Preferred embodiments are subject of the dependent claims.

Summary of the Invention

[10] The invention relates in a first aspect to novel organosulfur compounds of the formula (I)

Wherein X represents an oxygen atom or a methylene group, R ^{1 represents} a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, preferably a methyl group, R ^{2 represents} a hydrogen atom or a linear or branched alkyl group having 1-8 carbon atoms R ³ preferably represents a hydrogen atom, R ^{3 represents} a linear or branched alkyl radical having 1-8 carbon atoms, preferably a methyl group, R ^{4 represents} a hydrogen atom or a linear or branched alkyl radical having 1-8 carbon atoms, preferably a methyl group, R ⁵ is a hydrogen atom or a linear or branched alkyl radical having 1-8 carbon atoms, preferably a methyl group, or R ^{5 is} absent, Y is a hydrogen atom, a linear or branched alkyl radical having 1-8 carbon atoms or an acetyl group, or Y is omitted, wherein there is no bond or a single bond at the location of a dashed line between Oa atom and Cf atom, whereby in the presence of a single bond in formula (I) the group R ^{5 is} omitted, and wherein at the location of one of the dashed lines between S Atom and Cg atom or between S atom and Ch atom each bond or a single bond is present, with the proviso that at least one of the dashed bonds is present as a single bond, wherein in each case a single bond between S atom and the C atoms C _g and Ch in formula (I) the group Y is omitted.

[11] Here and below, the numbering of the positions in the molecule according to formula (I) is carried out and maintained consistently for uniform labeling. The Markush formulas X, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and Y each refer to functional radicals or radical groups, which are familiar to the expert.

[12] A preferred embodiment of the present invention relates to compounds of the formula (I), in all forms of their positional isomers, diastereomers and enantiomers, and mixtures thereof:

Formula (I) wherein R ^{1 represents} a hydrogen atom or a methyl, an ethyl, an iso-propyl or a butyl group.

[13] A further preferred embodiment of the present invention relates to compounds of formula (I) wherein R ^{1 represents} a methyl group. [14] An alternative preferred embodiment of the present invention relates to compounds of formula (I) wherein R ^{1 represents} a hydrogen atom or a methyl, an ethyl, an iso-propyl or a butyl group, R ^{2 is} a hydrogen atom and R ^{3 is} a methyl group.

[15] A further preferred embodiment of the present invention relates to compounds of the formula (I) in which R ^{1 represents} a methyl group, R ^{2 represents} a hydrogen atom and R ^{3 represents} a methyl group.

[16] A more preferred embodiment of the present invention relates to compounds of formula (I) wherein R ^{1 represents} a hydrogen atom or a methyl, an ethyl, an iso-propyl or a butyl group and X represents an oxygen atom.

[17] A further preferred embodiment of the present invention relates to compounds of the formula (I), wherein R ^{1 represents} a methyl group and X represents an oxygen atom.

[18] A preferred embodiment of the present invention relates to compounds of the formula (I) in which R ^{2 represents} a hydrogen atom or a methyl or an ethyl group.

[19] A further preferred embodiment of the present invention relates to compounds of the formula (I) in which R ^{2 represents} a hydrogen atom.

[20] An alternative more preferred embodiment of the present invention relates to compounds of formula (I) wherein R ^{2 represents} a hydrogen atom and X represents an oxygen atom.

[21] A further preferred embodiment of the present invention relates to compounds of the formula (I) in which R ^{2 represents} a hydrogen atom and X represents a -CH ² -methylene group. [22] A preferred embodiment of the present invention relates to compounds of formula (I) wherein R ^{3 represents} a hydrogen atom or a methyl, an ethyl, an iso-propyl or a butyl group.

[23] A further preferred embodiment of the present invention relates to compounds of formula (I) wherein R ^{3 represents} a methyl group.

[24] An alternative more preferred embodiment of the present invention relates to compounds of formula (I) wherein R ^{3 represents} a methyl group and X represents an oxygen atom.

[25] A further preferred embodiment of the present invention relates to compounds of formula (I) wherein R ^{3 represents} a methyl group and X represents a -CH 2 -methylene group.

[26] A preferred embodiment of the present invention relates to compounds of formula (I) wherein R ^{4 represents} a methyl, an ethyl, an iso-propyl or a butyl group.

[27] Another particularly preferred embodiment of the present invention relates to compounds of formula (I) wherein R ^{4 represents} a methyl group. Here, R ² is particularly preferably H, ie a hydrogen atom or hydrogen radical.

[28] An alternative more preferred embodiment of the present invention relates to compounds of formula (I) wherein R ^{4 represents} a methyl group and X represents an oxygen atom.

[29] A further preferred embodiment of the present invention relates to compounds of the formula (I) in which R ^{4 represents} a methyl group and X represents a -CH 2 -methylene group. [30] An alternative more preferred embodiment of the present invention relates to compounds of formula (I) wherein R ^{5 represents} a methyl, an ethyl, an iso-propyl or a butyl group and X represents a -CH 2 -methylene group.

[31] A further preferred embodiment of the present invention relates to compounds of the formula (I) in which R ^{5 represents} a methyl group or an ethyl group and X represents a -CH 2 -methylene group.

[32] A preferred embodiment of the present invention relates to compounds of formula (I) wherein Y represents a hydrogen atom or a methyl, an ethyl, an iso-propyl, a butyl or an acetyl group.

[33] A further preferred embodiment of the present invention relates to compounds of the formula (I), wherein Y represents a hydrogen atom or a methyl or acetyl group.

[34] An alternative more preferred embodiment of the present invention relates to compounds of formula (I) wherein Y represents a hydrogen atom and X represents an oxygen atom.

[35] A further preferred embodiment of the present invention relates to compounds of the formula (I), wherein Y represents a hydrogen atom and X represents a -CH 2 -methylene group.

[36] In a second aspect, the invention relates to compounds of the formula (II) in all forms of their positional isomers, diastereomers and enantiomers, and mixtures thereof:

Where X is an oxygen atom or a methylene group, R ^{1 is} a hydrogen atom or a linear or branched alkyl radical having 1 to 8 carbon atoms, preferably a methyl group, R ^{2 is} a hydrogen atom or a linear or branched alkyl radical having 1 R ^{3 represents} a linear or branched alkyl radical having 1-8 carbon atoms, preferably a methyl group, R ^{4 represents} a hydrogen atom or a linear or branched alkyl radical having 1-8 carbon atoms, preferably a methyl group, Y represents a hydrogen atom, a linear or branched alkyl radical having 1-8 carbon atoms or an acetyl group or Y is omitted, wherein at the location of one of the dashed lines between S atom and C ₈ - atom or between S atom and Ch atom respectively no bond or single bond is present, provided that at least one of the dashed bonds is present as a single bond, wherein in the presence of a single bond between the S atom and the C atoms C _g and Ch in formula (II) the group Y is omitted.

[37] The abovementioned preferred variants of X, R ¹ , R ² , R ³ , R ⁴ and Y for general formula (I) are also preferred for the specific embodiment of the invention of formula (II). In contrast to formula (I), however, in formula (II) the ring between Oa and Cf is closed and thus R ⁵ is omitted. This variant is advantageous according to the invention. [38] A preferred embodiment of the present invention relates to compounds of formula (II) wherein R ^{1 represents} a methyl group.

[39] An alternative preferred embodiment of the present invention relates to compounds of the formula (II) wherein R ^{1 represents} a hydrogen atom or a methyl, an ethyl, an iso-propyl or a butyl group, R ^{2 is} a hydrogen atom and R ^{3 is} a methyl group.

[40] A further preferred embodiment of the present invention relates to compounds of the formula (II) in which R ^{1 represents} a methyl group, R ^{2 represents} a hydrogen atom and R ^{3 represents} a methyl group.

[41] A more preferred embodiment of the present invention relates to compounds of formula (II) wherein R ^{1 represents} a hydrogen atom or a methyl, an ethyl, an iso-propyl or a butyl group and X represents an oxygen atom.

[42] A further preferred embodiment of the present invention relates to compounds of the formula (II), wherein R ^{1 represents} a methyl group and X represents an oxygen atom.

[43] A preferred embodiment of the present invention relates to compounds of formula (II) wherein R ^{2 represents} a hydrogen atom or methyl or an ethyl group.

[44] A further preferred embodiment of the present invention relates to compounds of the formula (II) in which R ^{2 represents} a hydrogen atom.

[45] An alternative more preferred embodiment of the present invention relates to compounds of formula (II) wherein R ^{2 represents} a hydrogen atom and X represents an oxygen atom.

[46] A further preferred embodiment of the present invention relates to compounds of the formula (II) in which R ^{2 represents} a hydrogen atom and X represents a -CH ² -methylene group. [47] A preferred embodiment of the present invention relates to compounds of formula (II) wherein R ^{3 represents} a hydrogen atom or a methyl, an ethyl, an iso-propyl or a butyl group.

[48] A further preferred embodiment of the present invention relates to compounds of the formula (II) in which R ^{3 represents} a methyl group.

[49] An alternative more preferred embodiment of the present invention relates to compounds of formula (II) wherein R ^{3 represents} a methyl group and X represents an oxygen atom.

[50] A further preferred embodiment of the present invention relates to compounds of the formula (II) in which R ^{3 represents} a methyl group and X represents a -CH 2 -methylene group.

[51] A preferred embodiment of the present invention relates to compounds of formula (II) wherein R ^{4 represents} a hydrogen atom or a methyl, an ethyl, an iso-propyl or a butyl group.

[52] Another particularly preferred embodiment of the present invention relates to compounds of formula (II) wherein R ^{4 represents} a methyl group. Here, R ² is particularly preferably H, ie a hydrogen atom or hydrogen radical.

[53] An alternative more preferred embodiment of the present invention relates to compounds of formula (II) wherein R ^{4 represents} a methyl group and X represents an oxygen atom.

[54] A further preferred embodiment of the present invention relates to compounds of the formula (II) in which R ^{4 represents} a methyl group and X represents a -CH 2 -methylene group. [55] A preferred embodiment of the present invention relates to compounds of the formula (II), wherein Y represents a hydrogen atom or a methyl, an ethyl, an isopropyl, a butyl or an acetyl group.

[56] A further preferred embodiment of the present invention relates to compounds of the formula (II), wherein Y represents a hydrogen atom or a methyl or acetyl group.

[57] An alternative more preferred embodiment of the present invention relates to compounds of formula (II) wherein Y represents a hydrogen atom and X represents an oxygen atom.

[58] A further preferred embodiment of the present invention relates to compounds of the formula (II), wherein Y represents a hydrogen atom and X represents a -CH 2 -methylene group.

[59] The compounds of formula (II) have an outstanding and unique odor profile containing i.a. green, fruity, citrus and tropical fruity notes. In addition, the compounds of the invention are convincing by an exceptionally strong odor intensity.

[60] In a third aspect, the invention relates to compounds of the formula (III):

Formula (III) wherein, X represents an oxygen atom or a methylene group, Is hydrogen or a linear or branched alkyl radical having 1 to 8 carbon atoms, preferably a methyl group, R ^{2 is} a hydrogen atom or a linear or branched alkyl radical having 1-8 carbon atoms, preferably a hydrogen atom, R ^{3 is} a linear or branched alkyl radical having 1 -8 carbon atoms, preferably a methyl group, R ⁴ represents a hydrogen atom or a linear or branched alkyl radical with 1 -8 carbon atoms, preferably a methyl group, R ⁵ represents a hydrogen atom, a linear or branched alkyl radical with 1 -8 carbon atoms, preferably a Y represents a hydrogen atom, a linear or branched alkyl radical having 1-8 carbon atoms or an acetyl group or Y is omitted, wherein at the location of one of the dashed lines between S atom and Cg atom or between S atom and Ch -Atom each bond or a single bond is present, with the proviso that ss at least one of the dashed bonds is present as a single bond, wherein in the presence of each of a single bond between the S atom and the C atoms C _g and Ch in formula (III) the group Y is omitted.

[61] The abovementioned preferred variants of X, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and Y for general formula (I) are also preferred for the specific embodiment of the invention of formula (III).

[62] A preferred embodiment of the present invention relates to compounds of the formula (III), wherein R ^{1 represents} a methyl group.

[63] An alternative preferred embodiment of the present invention relates to compounds of the formula (III), wherein R ^{1 represents} a hydrogen atom or a methyl, an ethyl, an iso-propyl or a butyl group, R ^{2 is} a hydrogen atom and R ^{3 is} a methyl group.

[64] A further preferred embodiment of the present invention relates to compounds of the formula (III) in which R ^{1 represents} a methyl group, R ^{2 represents} a hydrogen atom and R ^{3 represents} a methyl group. [65] A more preferred embodiment of the present invention relates to compounds of formula (III) wherein R ^{1 represents} a hydrogen atom or a methyl, an ethyl, an iso-propyl or a butyl group and X represents an oxygen atom.

[66] A further preferred embodiment of the present invention relates to compounds of the formula (III), wherein R ^{1 represents} a methyl group and X represents an oxygen atom.

[67] A preferred embodiment of the present invention relates to compounds of the formula (III) in which R ^{2 represents} a hydrogen atom or a methyl or an ethyl group.

[68] A further preferred embodiment of the present invention relates to compounds of the formula (III) in which R ^{2 represents} a hydrogen atom.

[69] An alternative more preferred embodiment of the present invention relates to compounds of formula (III) wherein R ^{2 represents} a hydrogen atom and X represents an oxygen atom.

[70] A further preferred embodiment of the present invention relates to compounds of the formula (III) in which R ^{2 represents} a hydrogen atom and X represents a -CH ² -methylene group.

[71] A preferred embodiment of the present invention relates to compounds of formula (III) wherein R ^{3 represents} a hydrogen atom or a methyl, an ethyl, an iso-propyl or a butyl group.

[72] A further preferred embodiment of the present invention relates to compounds of the formula (III) in which R ^{3 represents} a methyl group.

[73] An alternative more preferred embodiment of the present invention relates to compounds of formula (III) wherein R ^{3 represents} a methyl group and X represents an oxygen atom. [74] A further preferred embodiment of the present invention relates to compounds of the formula (III) in which R ^{3 represents} a methyl group and X represents a -CH 2 -methylene group.

[75] A preferred embodiment of the present invention relates to compounds of formula (III) wherein R ^{4 represents} a hydrogen atom or a methyl, an ethyl, an iso-propyl or a butyl group.

[76] A further particularly preferred embodiment of the present invention relates to compounds of the formula (III) in which R ^{4 represents} a methyl group. Here, R ² is particularly preferably H, ie a hydrogen atom or hydrogen radical.

[77] An alternative more preferred embodiment of the present invention relates to compounds of formula (III) wherein R ^{4 represents} a methyl group and X represents an oxygen atom.

[78] A further preferred embodiment of the present invention relates to compounds of the formula (III) in which R ^{4 represents} a methyl group and X represents a -CH 2 -methylene group.

[79] An alternative preferred embodiment of the present invention relates to compounds of the formula (III) wherein R ⁵ is a methyl, an ethyl, an isopropyl or a butyl group and X represents a -CH2- methyl group.

[80] A further preferred embodiment of the present invention relates to compounds of the formula (III) in which R ^{5 represents} a methyl group or an ethyl group and X represents a -CH 2 methylene group.

[81] A preferred embodiment of the present invention relates to compounds of formula (III) wherein Y represents a hydrogen atom or a methyl, an ethyl, an iso-propyl, a butyl or an acetyl group. [82] A further preferred embodiment of the present invention relates to compounds of the formula (III), wherein Y represents a hydrogen atom or a methyl or acetyl group.

[83] An alternative more preferred embodiment of the present invention relates to compounds of formula (III) wherein Y represents a hydrogen atom and X represents an oxygen atom.

[84] A further preferred embodiment of the present invention relates to compounds of the formula (III), wherein Y represents a hydrogen atom and X represents a -CH 2 -methylene group.

[85] In contrast to the formula (I), however, in formula (III) the ring between Oa and Cf is open and thus R ^{5 has} to be defined. Preferably, R ⁵ = -Me or -Et. This open-chain variant is also advantageous according to the invention.

[86] The compounds of the formula (III) have in particular strong fruity notes.

[87] The compounds of formula (I) or of formula (II) or (III) may be in various forms, corresponding to the possible enantiomers, diastereomers and positional isomers of formula (I). Although some of these possible compounds are preferred, as explained below, but basically the invention encompasses all forms of the isomers of formula (I), (II) or (III), as well as the diastereomeric and enantiomeric mixtures thereof.

[88] In a preferred fourth variant of the present invention, the novel organosulfur compounds of the formula (I), (II) or (III) are in the form of a position isomer mixture of the two compound variants each having a single bond of the C atoms C _g or Ch to the S atom before. However, the position isomer with S bond to the C atom C _g is particularly preferred. These are particularly odor intensive.

The invention preferably relates to organosulfur compounds of the formula (II), wherein the compounds in the form of a position isomer mixture of the two compound variants can each be present with a single bond of the carbon atoms C _g or Ch to the S atom, however, the position isomer with S bond to the C atom C _g is particularly preferred.

Preference is given to novel organosulfur compounds of the formula (III), where the compounds may be present in the form of a position isomer mixture of the two compound variants each having a single bond of the carbon atoms C _g or Ch to the S atom, but particularly preferred the position isomer with S-bonding to the C atom C _g .

[91] A further preferred fifth aspect of the present invention relates to compounds of the formula (I), (II) or (III), wherein the compounds are in the form of a diastereomeric mixture having stereocenters at two or more of the positions selected from the group consisting of : Cd, Cf, _Cg , Ch.

[92] A further preferred variant of the present invention relates to compounds of the formula (III) where the compounds are in the form of the diastereomers or of a diastereomeric mixture having stereocenters at the position Cd, _Cg and optionally Ch (when R ^{3 is} different from R ⁴ and both each not equal to -H).

[93] Preferably, the compounds of formula (II) stereogenic centers at all three positions Cd, and C Cf _g.

[94] In a particular variant of the invention: R ¹ = -Me, R ² = -H, R ³ = -Me, R ⁴ = -Me and Y = -H. Here, too, the compound of formula (II) stereogenic centers at all three positions Cd, Cf and C _g and all isomers, that diastereomers and enantiomers of the formula (IIa) (below) are encompassed by the invention.

Formula (IIa)

[95] In this case, the preferred positional isomer is the carbon with the thiol group on the C _g . Furthermore, as an alternative X = O, this then gives a 1,3-dioxacyclohexane ring. However, particularly preferred is X = Chb and the ring is a pyran after compound 7:

Connection 7

[96] The abovementioned compounds of general formula (IIa) and in particular compound 7 are strongly odorous compounds which, depending on the isomer mixtures, have a fruity, exotic fruity, guava or agrumenic or green and sulphurous odor.

[97] A preferred sixth aspect of the present invention relates to compounds of the formula (I) wherein the compounds are configured at the position Cd (R) -.

[98] Particular preference is given to compounds of the formula (II) in which the compounds are present in the position Cd (R) -configured. It should be noted that in the case of the compound according to formula (III) some compounds in the open-chain Variant changes the stereopriority of the residues at the center Cd, so that here in the same stereochemical arrangement, the Cd (S) configuration is preferred.

[99] An alternative preferred variant of the present invention therefore relates to compounds of the formula (IIa) which are present at position Cd as (R) -configured isomers 8.

Connection 8

[100] These are characterized by a concise odor profile.

[101] In a seventh further development, the compounds of the formula (I) are in the position Cd (R) -configured and present at the position Cf (S) -configured.

[102] Particularly preferred are the compounds of formula (II) wherein Cd {R) ~ is present at the position and Cf (S) is at the position. These variants according to compound 9 are also distinguished by a strong odor profile.

Connection 9 An eighth aspect of the invention relates to compounds of the formula (I) where the compounds are present in the form of a cis: trans isomeric mixture at the positions Cd: Cf, and the cis configuration is predominantly present.

[103] In this case, preference is given to compounds of the formula (I) in which a cis configuration of the thiorosenoxides is present at the positions Cd: Cf. Furthermore, the ratio cis: trans is preferably from 60:40 to 90:10. Particular preference is given to compounds of the formula (I) with the ratio cis: trans greater than 9: 1. Furthermore, compounds of the formula (I) with the ratio cis: trans greater than 95: 5 are particularly preferred.

[104] For the purposes of the invention, therefore, compounds of the formula (II) which are cis-configured at the positions Cd and Cf are particularly preferred, with the ratio cis: trans being from 60:40 to 90:10. They have intensified odor profiles of fruity, exotic fruity, guava, citrus, green and sulphurous. This is especially true for compounds 7, 8 and 9 with the cis: trans ratios mentioned above.

[105] Especially preferred are compounds of formula (II) with the ratio cis: trans greater than 90:10. Furthermore, compounds of the formula (II) with the ratio cis: trans are greater than 95: 5.

[106] Manufacturing process

[107] In a further ninth aspect of the invention, this comprises a production process for the sulfurization of rose oxide.

[108] As will be explained in more detail below, the compounds of the formula (I), (II) or (III) according to the invention can be synthesized by a process comprising at least the steps (i), (ii) and (iii). For this purpose, it is assumed that the corresponding rose oxide starting material of the formula (IV), where the compound of the formula (IV):

 Formula (IV)

(i) is reacted with thioacetic acid, preferably with free-radical catalysis, in order to obtain, with a regioselectivity of greater than or equal to 95%, the compound of the formula (V):

 Formula (V)

(ii) optionally subsequently cleaving off the acetyl group to obtain the following compound of formula (VI):

 Formula (VI)

(iii) and optionally thereafter alkylating the thiol group, preferably methylated, to obtain the compounds (I), (II) or (III), wherein the groups X, Y, R ¹ , R ² , R ³ , R ⁴ and R ⁵ and the dashed lines each have the meanings given in the first aspect of the invention.

In step (i) of the process according to the invention, the compound of formula (V) is preferably formed in relation to the compound of formula (Vb), as shown below, preferably in a ratio greater than 95: 5, more preferably in one Ratio greater 98: 2.

 Formula (Vb)

[110] Particularly preferred in step (i) is the use of thioacetic acid with azobis (isobutyronitrile) (AIBN).

[111] In step (ii) of the process of the invention, the compound of formula (VI) is preferably formed relative to the compound of formula (VIb), as shown below. When step (ii) is performed directly following (i) takes place, the product Gennisch with the formula (VI) in relation to the formula (Vlb) is preferably in a ratio greater than 95: 5, more preferably in a ratio greater than 98: 2.

 Formula (VIb)

Particularly preferred in step (ii) is the use of K 2 CO 3 with methanol

[113] In step (iii) it is preferable to alkylate such that the radical radicals are Y = -Ac, -Me or -Et. For this purpose, common alkylating agents can be used. Particularly preferred is methyl iodide with NaH in THF.

The steps (i), (ii) and (iii) according to the invention are ideally carried out successively in the order given, additional intermediate steps being possible.

[115] A preferred variant of the present invention relates to the synthesis of 2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propane-1-thiol 8, which is one of the central compounds of the invention.

 11 12

Odor description of S- [2-methyl-1 - [(4R) -4-methyltetrahydropyran-2 yl] propyl] ethaneethioate 12: gum, garlic, sulphurous.

 12 8

[117] Odor description of 2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propane-1-thiol 8: strong, fruity, tropical fruit, guava, grapefruit, green, sulphurous. Taste description: Passion fruit (25 ppm in 5% sucrose), sulphurous (25 ppm in 0.5% saline).

[118] Synthesis of 4-methyl-2- (2-methyl-1-methylsulfanyl-propyl) tetrahydropyran 27

 8 27

[119] Odor description of 4-methyl-2- (2-methyl-1-methylsulfanyl-propyl) tetrahydropyran 27: spicy, garlic, pungent, green.

[120] In a further tenth aspect of the invention, a production process for the sulfurization of rose oxide is described in order to prepare the thiirane variants of the compounds of the formula (I), (II) or (III) according to the invention. This process comprises at least the steps (i) and (ii) in which the double bond of the corresponding starting material of the formula (IV):

 Formula (IV)

(i) is epoxidized with a peracid, preferably with meta-chloroperbenzoic acid,

(ii) and then reacting the oxirane formed under (i), preferably with ammonium thiocyanate, to give the thiirane of the formula (VII) below:

Formula (VII) wherein the groups X, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each have the meaning given in the first aspect.

[121] As an example, the preferred synthesis of 2- (3,3-dimethylthiiran-2-yl) -4-methyl-tetrahydropyran 29 is based on 30.

30

The compound becomes 4-methyl-2- (2-methylprop-1-enyl) tetrahydropyran (rose oxide) dissolved and reacted with mefa-chloroperbenzoic acid to give the crude product 2- (3,3-dimethyloxiran-2-yl) -4-methyl-tetrahydropyran 30.

 The obtained 2- (3,3-dimethyloxiran-2-yl) -4-methyl-tetrahydropyran 30 is mixed with ammonium thiocyanate and cerium (IV) ammonium nitrate. There is obtained 2- (3,3-dimethylthiiran-2-yl) -4-methyl-tetrahydropyran 29 as a colorless liquid. Compound 29 is obtained as a mixture of cis-29 / trans-29.

[122] Odor description of the isomers 2- (3,3-dimethylthiiran-2-yl) -4-methyltetrahydropyran obtained as a mixture 29: rose, gum, green. The molecular num- bering can be done below according to the IUPAC priority.

AND enantiomer AND enantiomer

 cis-29 trans-29

[123] The most preferred compounds of formula (I), (II) or (III) are listed below:

2-Methyl-1- (4-methyltetrahydropyran-2-yl) propane-1-thiol 7,2-Methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propane-1-thiol 8, S- [2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propyl] -ethanethioate 12, 2-methyl-1- (4-methyltetrahydropyran-2-yl) propane-1-thiol 17, 2-methyl-1 - [(4S) -4-methyltetrahydropyran-2-yl] propane-1-thiol 18, S- (1-isopropyl-6-methoxy-4-methyl-hexyl) ethanethioate 19, 8- methoxy 2,6-dimethyl-octane-3-thiol 20, 2-methyl-1- (4-methyl-1,3-dioxan-2-yl) -propane-1-thiol 21, S- [2-methyl-1 - (4-methyl-1,3-dioxan-2-yl) propyl] ethanethioate 22, 4-methyl-2- (2-methylallyl) -1, 3-dioxane 23, 3- (4-methyl-1, 3- dioxan-2-yl) butan-2-thiol 24, S- [1- (1, 3-dioxan-2-yl) -2-methyl-propyl] ethaneethioate 25, 1- (1,3-dioxan-2-yl) yl) -2-methylpropane-1-thiol 26, 4-methyl-2- (2-methyl-1-methylsulfanyl-propyl) tetrahydropyran 27, 2- (3,3-dimethylthiiran-2-yl) -4- Methyl tetrahydropyran 29.

[124] The compounds of formula (I), (II) or (III), and their isomer mixtures are suitable as fragrances and flavorings, or as additives for fragrance mixtures. Further use find these substances in consumer goods containing these compounds and mixtures.

[125] The compounds of formula (I), (II) or (III) are generally novel strong odorants and flavorings. Odor or taste sensations vary from substance to substance. Special stimuli are described below

A further eleventh aspect of the present invention relates to fragrances or flavorings which comprise compounds according to the invention, in particular of the formulas (I) to (VII), in particular according to (I), (II) or (III). This is also one of the main applications of these substances and compounds according to the invention.

[127] Because of their olfactory properties, the compounds of the formulas (I) to (VII) according to the invention are outstandingly suitable for use in fragrance or flavor mixtures. The compounds can be used as a single substance or combined with a variety of other fragrances in numerous products. Particularly advantageously, the compounds can be combined with other fragrances in different, different proportions to novel perfume compositions (as a special fragrance mixtures).

[128] Preferably, the compounds can also be combined with other flavorings in various proportions to form novel flavor compositions as special flavor mixtures. [129] In a twelfth development of the present invention, Riechoder relates to flavorings comprising a fragrance or flavoring agent according to the invention, especially of formulas (I) to (VII), in particular to (I), (II) or (III), and furthermore comprise one or more additional fragrances and / or flavorings.

Examples of fragrances with which the compounds according to the invention are advantageously combined are found, for example, in US Pat. In "S. Arctander, Perfume and Flavor Chemicals, Vol. I and II, Montclair, N.J., 1969, Selbstverlag or H. Surburg and J. Panten, Common Fragrance and Flavor Materials, 5th Ed., Wiley-VCH, Weinheim, 2006. The following extracts from natural raw materials and individual fragrances are mentioned in detail:

[131] Extracts from natural raw materials: essential oils, concretes, absolues, resines, resinoids, balms, tinctures such as. B. amber tincture; Amyrisöl; Angelica seed oil; Angelica root oil; anise oil; Valerian oil; Basil oil; Tree moss - absolute; Bay oil; Mugwort oil; Benzoeresin; Bergamot oil; Beeswax absolute; birch tar; Bitter almond oil; Savory oil; Buccoblätteröl; Cabreuvaöl; cade oil; calamus; camphor oil; Cananga oil; cardamom; Cascarillaöl; cassia; Cassie absolute; Beaver-absolue; Cedernblätteröl; cedarwood; cistus; citronella; lemon; copaiba balsam; Copaivabalsamöl; Coriander oil; costus root; Cuminöl; Cypress oil; Davanaöl; Dill herb oil; Dill seed oil; Eau de Brouts absolute; Oak moss absolute; elemi; Tarragon oil; Eucalyptus citriodora oil; eucalyptus oil; Fennel oil; Pine needle oil; galbanum; Galbanumresin; geranium; Grapefruit oil; guaiac wood; gurjun balsam; gurjun balsam oil; Helichrysum absolute; Helichrysumöl; Ginger oil; Iris root absolute; Orris root oil, Jasmine absolute; calamus, Chamomile oil blue; Camomile oil Roman; Carrot seed oil; Kaskarillaöl; Pine needle oil; spearmint; Seed oil; labdanum; Labdanum absolute; Labdanumresin; Lavandine absolute; Lavandin oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Distilled lime oil; Pressed lime oil; linaloe; Litsea cubeba oil; Bay leaf oil; Macisöl; Marjoram oil; Mandarin oil; Massoirindenöl; Mimosa absolute; Musk grain oil; musk tincture, Clary sage oil; nutmeg; Myrrh absolute; Myrrh oil; myrtle; Clove leaf oil; Clove flower oil; neroli; Olibanum absolute; olibanum; Opopanaxöl; Orange blossom absolute; Orange oil; oregano; Palma pink oil; patchouli oil; perilla oil; Peruvian balsam oil; Parsley leaf oil; Parsley seed oil; Petitgrain oil; Peppermint oil; Pepper oil; chilli; pine oil; Poleyöl; Rose absolute; Rosewood oil; Rose oil; Rosemary oil; Sage oil Dalmatian; Sage oil spanish; sandalwood; Celery seed oil; spike lavender oil; star anise; Styraxöl; tagetes; Pine needle oil; Tea-tree-oil; turpentine; Thyme oil; Tolu; Tonka absolute; Tube roses absolute; Vanilla extract; Violet leaf absolute; verbena; vetiver; Juniper berry oil; Wine yeast oil; Wormwood oil; Wintergreen oil; ylang oil; hyssop oil; Zibet Absolute; cinnamon leaf; Cinntrindenol and fractions thereof, or ingredients isolated therefrom;

[132] Individual fragrances from the following groups:

[133] hydrocarbons, e.g. 3-carene; α-pinene; beta-pinene; a-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E, Z) -1, 3,5-undecatriene; styrene; diphenylmethane;

[134] aliphatic alcohols such as e.g. hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E) -2-hexenol; (E) - and (Z) -3-hexenol; 1-octen-3-ol; Mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E, Z) -2,6-Nonadienol; 3,7-dimethyl-7-methoxy-octan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol;

[135] aliphatic aldehydes and their acetals, e.g. hexanal; heptanal; octanal, nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E) -2-hexenal; (Z) -4-heptenal; 2.6-dimethyl-5-heptenal; 10- undecenal; (E) -4-decenal; 2-dodecenal; 2,6,10-trimethyl-9-undecenal; 2,6,10-trimethyl-5,9-undecadienal; Heptanaldiethylacetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde; 1 - (1-methoxy-propoxy) - (E / Z) -3-hexene;

[136] aliphatic ketones and their oximes such as 2-heptanone; 2-octanone; 3- Octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one; [137] aliphatic sulfur compounds such as 3-methylthio-hexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-Menthene-8-thiol;

[138] aliphatic nitriles, e.g. 2-nonenoic acid nitrile; 2-Undecensäurenitril; 2-tridecenoic acid nitrile; 3,12-Tridecadiensäurenitril; 3,7-dimethyl-2,6-octadiene-acid nitrile; 3,7-dimethyl-6-octensäurenitril;

[139] esters of aliphatic carboxylic acids, e.g. (E) - and (Z) -3-hexenylformate; ethylacetoacetate; isoamyl; hexyl acetate; 3,5,5-Thmethylhexylacetat; 3-methyl-2-butenyl acetate; (E) -2-hexenyl acetate; (E) - and (Z) -3-hexenylacetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; Butyl butyrate, isoamyl; hexyl butyrate; (E) - and (Z) -3-hexenyl isobutyrate; hexyl crotonate; Ethylisovalerianat; Ethyl 2-methylpentanoate; ethylhexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; Ethyl (E, Z) -2,4-decadienoate; Methyl-2-octinat; Methyl 2-noninate; Allyl-2-isoamyloxyacetat; Methyl 3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl crotonate;

[140] acydic terpene alcohols, such as. Citronellol; geraniol; nerol; linalool; Lavadulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octene-2-ol; 2,6-dimethyl octane-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadiene-2-ol; 3,7-dimethyl-4,6-octadiene-3-ol; 3,7-dimethyl-1, 5,7-octatrien-3-ol 2,6-dimethyl-2,5,7-octathen-1-ol; as well as their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates;

[141] acydic terpene aldehydes and ketones, such as B. Geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-thymethyl-9-undecenal; geranyl acetone; and the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal;

[142] cyclic terpene alcohols, such as. Menthol; isopulegol; alpha-terpineol; Terpinenol-4; Menthane-8-ol; Menthan-1-ol; Menthane-7-ol; borneol; soborneol; linalool; monopoly; cedrol; ambrinol; Vetyverol; guaiol; and their formates, Acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates;

[143] the cyclic terpene aldehydes and ketones, such as. Eg menthone; Isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchon; alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethyl-ionone; alpha-lron; alpha-damascone; beta-damascone; beta-damascenone; delta-damascone; gamma-damascone; 1 - (2,4,4-trimethyl-2-cyclohexene-1-yl) -2-butene

1 - on; 1, 3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalene-8 (5H) -one; 2-methyl-4- (2,6, 6-trimethyl-1-cyclohexene-1-yl) -2-butenal; Nootkatone; Dihydronootkaton; 4,6,8-Mega stigma Then-3-one; alpha-sinensal; beta-Sinensal; acetylated cedarwood oil (methyl cedryl ketone);

[144] cyclic alcohols, e.g. 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-lsocamphylcyclohexanol; 2,6,9-thymethyl-Z2, Z5, E9-cyclododecatriene-1-ol;

2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

[145] cycloaliphatic alcohols, e.g. alpha, 3,3-

Thmethylcyclohexylnethanol; 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) -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-trin-ethyl-3-cyclopent-1-yl) -4-penten-2-ol; 1 - (2,2,6-trimethylcyclohexyl) pentan-3-ol; 1 - (2,2,6-

Thmethylcyclohexyl) hexan-3-ol;

[146] cyclic and cycloaliphatic ethers, e.g. cineol; Cedrylnnethylether; Cyclododecyl methyl ether; 1, 1-dimethoxycyclododecane;

 (Ethoxymethoxy) cyclododecane; alpha-Cedrenepoxid; 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-cyclohexene-1-yl) -5-methyl-5- (1-methylpropyl) -1,3-dioxane;

[147] cyclic and macrocyclic ketones, such as 4-tert-butylcyclohexanone; 2,2,5-Trinnethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentyl-cyclopentanone; 2-hydroxy-3-methyl-2-cyclopentene-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopentene-1-one; 3-methyl-4-cyclopentanecenone; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4- (1-ethoxy-vinyl) -3,3,5,5-tetramethylcyclohexanone; 4-tert.-pentylcyclohexanone; 5-cyclohexa-decene-1-one; 6,7-dihydro-1,1,3,3,3-pentanethyl-4 (5H) -indanone; 8-Cyclohexadecen-

1 - on; 9-cycloheptadecene-1-one; cyclopentadecanone; cyclohexadecanone;

[148] cydoaliphatic aldehydes, e.g. 2,4-dimethyl-3-cyclohexene carbaldehyde;

2-methyl-4- (2,2,6-thmethyl-cyclohexene-1-yl) -2-butenal; 4- (4-hydroxy-4-methylpentyl) -

3-cyclohexene carbaldehyde; 4- (4-methyl-3-penten-1-yl) -3-cyclohexene carbaldehyde;

[149] cydoaliphatic ketones, such as. B. 1 - (3,3-dimethylcyclohexyl) -4-penten-1-one; 2,2-dimethyl-1 - (2,4-dimethyl-3-cyclohexene-1-yl) -1-propanone; 1 - (5,5-dimethyl-1-cyclohexene-1-yl) -4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone; Methyl-2,6,10-thmethyl-2,5,9-cyclododecatnenylketon; tert-butyl (2,4-dimethyl-3-cyclohexene-1-yl) ketone;

[150] esters of cyclic alcohols, e.g. 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; Decahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; Decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5, and 6-indenyl acetate, respectively; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5, and 6-indenylpropionate, respectively; 4,7-methano-3a, 4,5,6,7,7a-hexahydro-5, and 6-indenyl isobutyrate, respectively; 4,7-Methanooctahydro-5, or 6-indenyl acetate;

[151] esters of cydoaliphatic alcohols, e.g. 1-cyclohexylethyl crotonate;

[152] esters of cydoaliphatic carboxylic acids, such as. For example, allyl-3-cyclohexylpropionate; Allylcyclohexyloxyacetat; cis and trans methyldihydrojasmonate; egg and trans methyl jasmonate; Methyl-2-hexyl-3-oxocyclopentanecarboxylate; Ethyl 2-ethyl-6,6-dimethyl-2-cyclohexene carboxylate; Ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; Ethyl 2-methyl-1,3-dioxolane-2-acetate; [153] araliphatic alcohols such as benzyl alcohol; 1-phenylethyl alcohol; 2-phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3- (3-nnethylphenyl) propanol; 1,1-dimethyl-2-phenylethyl alcohol; 1, 1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenyl-propanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propene-1-ol; 4-methoxybenzyl; 1 - (4-isopropylphenyl) ethanol;

[154] esters of araliphatic alcohols and aliphatic carboxylic acids, e.g. benzyl acetate; benzylpropionate; benzyl isobutyrate; Benzylisovalerianat, 2-phenylethyl acetate; 2-phenylethyl propionate; 2-Phenylethylisobutyrat; 2-phenylethyl isovalerate; 1-phenylethyl acetate; alpha-Trichlormethylbenzylacetat; alpha, alpha-dimethylphenylethyl acetate; alpha, alpha-dimethylphenylethyl butyrate; cinnamyl; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;

[155] araliphatic ethers, such as 2-phenylethyl; 2-phenylethyl isoamyl ether; 2-phenylethyl-1-ethoxyethyl ether; Phenylacetaldehyde dimethylacetal; phenylacetaldehyde; Hydratropaaldehyddimethylacetal; Phenylacetaldehydglycerinacetal; 2,4,6-thymethyl-4-phenyl-1,3-dioxane; 4,4a, 5,9b-tetrahydroindeno [1,2-d] -m-dioxin; 4,4a, 5,9b-tetrahydro-2,4-dimethyl-indeno [1,2-d] -m-dioxin;

[156] aromatic and araliphatic aldehydes, such as. B. benzaldehyde; Phenylacetaldehyde; 3-phenylpropanal; Hydratropaaldehyd; 4-methylbenzaldehyde; 4-methyl-phenylacetaldehyde; 3- (4-ethylphenyl) -2,2-dimethylpropanal; 2-methyl-3- (4-isopropylphenyl) propanal; propanal, 2-methyl-3- (4-tert-butylphenyl); 2-methyl-3- (4-isobutylphenyl) propanal; 3- (4-tert-butylphenyl) propanal; cinnamic aldehyde; alpha-butylcinnamaldehyde; alpha-amyl cinnamic aldehyde; -alpha hexyl cinnamic aldehyde; 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;

[157] aromatic and araliphatic ketones, such as acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4 Phenyl-2-butanone; 4- (4-hydroxyphenyl) -2-butanone; 1 - (2-naphthalenyl) ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl) ethanone; benzophenone; 1, 1, 2,3,3,6-hexamethyl-5-indanylmethyl ketone; 6-tert-butyl-1, 1-dimethyl-4-indanyl methyl ketone; 1 - [2,3-dihydro-1, 1, 2,6-tetramethyl-3- (1-methylethyl) -1H-5-indenyl] ethanone; 5 ', 6', 7 ', 8'-tetrahydro-3', 5 ', 5', 6 ', 8', 8'-hexanethyl-2-acetonaphthone;

[158] aromatic and araliphatic carboxylic acids and their esters, e.g. benzoic acid; phenylacetic acid; methylbenzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate, methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; Methylcinnmat; ethylcinnamate; Benzyl; Phenyl ethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; Isoamyl salicylate; hexyl salicylate; cyclohexyl, Cis-3-hexenyl salicylate; benzyl; phenylethyl; Methyl-2,4-dihydroxy-3,6-dimethylbenzoate; Ethyl 3-phenyl-glycidate; Ethyl-3-methyl-3-phenylglycidate;

[159] nitrogen-containing aromatic compounds, e.g. 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert.-butylacetophenone; cinnamic acid; 3-methyl-5-phenyl-2-pentensäurenitril; 3-methyl-5-phenylpentanenitrile; methyl anthranilate; Methyl N-methylanthranilate; Schiff's bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3- (4-tert-butylphenyl) propanal or 2,4-dimethyl-3-cyclohexene carbaldehyde; 6-isopropylquinoline; 6-lsobutylchinolin; 6-sec.-butylquinoline; 2- (3-phenylpropyl) pyridine; indole; skatol; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;

[160] phenols, phenyl ethers and phenyl esters, e.g. estragole; anethole; eugenol; Eugenylmethylether; isoeugenol; Isoeugenylmethylether; thymol; carvacrol; diphenyl ether; beta naphthyl methyl ether; beta-Naphthylethylether; beta-naphthyl isobutyl ether; 1, 4-dimethoxybenzene; Eugenylacetat; 2-methoxy-4-methyl phenol; 2-ethoxy-5- (1-propenyl) phenol; p-Kresylphenylacetat;

[161] heterocyclic compounds, such as 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one; [162] lactones, such as 1, 4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1, 4-decanolide; 8-decene-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1, 5-decanolide; 1, 5-dodecanolide; 4-methyl-1,4-decanolide; 1,15-pentadecanolide; cis and trans-1 1-pentadecene-1, 15-olide; cis- and trans-12-pentadecene-1, 15-olide; 1, 16-hexadecanolide; 9-hexadecene-1, 16-olide; 10-oxa-1, 16-hexadecanolide; 1 1 -Oxa-1, 16-hexadecanolide; 12-oxa-1,16-hexadecanolide; Ethylene-1,12-dodecanedioate; Ethylene-1,13-tridecanedioate; coumarin; 2,3-dihydrocoumarin; Octahydrocoumarin.

[163] The compounds according to the invention can be advantageously combined with other flavorings.

A further thirteenth variant of the invention relates to fragrance or flavor mixtures, wherein the total amount of the compounds (I) to (VII) according to the invention, in particular according to (I), (II) or (III), based on the total weight of the fragrance or flavor mixture 0.00001 to 5% by weight, preferably 0.00001 to 1 wt .-%, and particularly preferably 0.0005 to 0.01 wt .-% is.

Especially preferred in perfume oil compositions of perfume mixtures is the amount of compounds (I) to (VII) according to the invention, in particular of (I), (II) or (III), in the range from 0.00001 to 5% by weight .-%, preferably 0.00001 to 1 wt .-% and particularly preferably 0.0005 to 0.01 wt .-%, based on the total perfume oil composition.

[166] For some applications, it is advantageous to use the compounds (I) to (VII) according to the invention, in particular perfume oils (fragrance mixtures) which are adsorbed according to (I), (II) or (III), on a carrier which is suitable both for a fine distribution of the fragrances in the product as well as a controlled release during use ensures.

[167] An alternative further fourteenth aspect of the invention relates to a perfumed product comprising a fragrance or a fragrance mixture according to the invention (especially according to the eleventh aspect) and a supplement, preferably a carrier, wherein the carrier comprises one or more substances comprises, selected from the following group: porous inorganic materials such as light sulphate, silica gels, zeolites, gypsum, clays, clay granules, aerated concrete etc. or organic materials such as woods, cellulose-based substances, sugars or plastics such as PVC, polyvinyl acetates or polyurethanes.

Particularly advantageous and therefore preferred in the context of the present invention is a perfumed product which contains one of the following compounds: 2-methyl-1- (4-methyltetrahydropyran-2-yl) propane-1-thiol 7,2-methyl-1 - (4R) -4-methyltetrahydropyran-2-yl] propane-1-thiol 8, S- [2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propyl] ethaneethioate 12, 2-methyl -1- (4-methyltetrahydropyran-2-yl) propane-1-thiol 17, 2-Methyl-1 - [(4S) -4-methyltetrahydropyran-2-yl] propane-1-thiol 18, p - (1-isopropyl-6-methoxy-4-methyl-hexyl) ethanethioate 19, 8-methoxy-2,6-dimethyl-octane-3-thiol 20, 2-methyl-1 - (4-methyl-1, 3 -dioxan-2-yl) propan-1-thiol 21, S- [2-methyl-1- (4-methyl-1,3-dioxan-2-yl) -propyl] -ethanethioate 22, 4-methyl-2- ( 2-methylallyl) -1,3-dioxane 23,3- (4-methyl-1,3-dioxan-2-yl) butane-2-thiol 24, S- [1- (1,3-dioxane-2- yl) -2-methyl-propyl] ethanethioate 25, 1- (1,3-dioxan-2-yl) -2-methyl-propane-1-thiol 26, 4-methyl-2- (2-methyl-1 - methylsulfanyl-propyl) tetrahydropyran 27, 2- (3,3-dim ethylthiiran-2-yl) -4-methyl-tetrahydropyran 29 and a supplement, preferably a carrier, wherein the carrier comprises one or more substances. Such carriers may be porous inorganic materials such as light sulfate, silica gels, zeolites, gypsum, clays, clay granules, aerated concrete, etc., or organic materials such as woods, cellulosic based materials, sugars or plastics such as PVC, polyvinyl acetates or polyurethanes.

[168] According to a preferred embodiment of the present invention, in perfume oil compositions (= perfume mixtures) adsorbed on a carrier, the amount of the inventive compounds of the formula (I) to (VII) used is usually in the range of 0.00001 to 5 wt .-%, preferably 0.00001 to 1 wt .-% and particularly preferably 0.0005 to 0.01 wt .-%, based on the total perfume oil composition.

[169] A further preferred embodiment of the present invention relates to a perfumed product which comprises a fragrance or a fragrance mixture or the perfumed product, the compounds of the formula (I) according to the invention. bis (VII), in particular according to (I), (II) or (III), and one or more additives.

Another fifteenth embodiment of the invention relates to a perfumed product comprising a fragrance or a fragrance mixture according to the invention or the perfumed product according to the invention as described above further comprising one or more additives selected from the following group: preservatives, abrasives, antiacne agents Anti-aging, anti-bacterial, anti-cellulite, anti-dandruff, anti-inflammatory, anti-irritant, anti-irritant, antimicrobial, antioxidant, astringent, antiperspirant, antiseptic, antistatic, binder, buffer, excipients, chelating agents, cell stimulants, cleansers, nourishing agents, depilatory agents, surface-active substances, deodorants, antiperspirants, emollients, emulsifiers, enzymes, essential oils, fibers, film formers, fixatives, foaming agents, foam stabilizers, Su foaming inhibitors, foaming boosters, fungicides, gelling agents, gelling agents, hair care products, hair styling agents, hair relaxants, moisturizing, moisturizing, moisturizing, moisturizing, bleaching, strengthening, stain removing, optically brightening, impregnating, antisoiling agents, anti-friction agents, lubricants, moisturizing creams, ointments, opacifiers, plasticizing agents, occlusive agents, polishes, brighteners, polymers, powders, proteins, moisturizers, abrasives, slilcones, skin soothers, skin cleansers, skin care agents, skin-healing agents, skin lightening agents, skin-protecting agents Antacids, cooling agents, skin cooling agents, warming agents, skin warming agents, stabilizers, UV absorbing agents, UV filters, detergents, fabric softeners, suspending agents, skin tanning agents, dil thickeners, vitamins, oils, waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, α-hydroxy acids, polyhydroxy fatty acids, plasticizers, dyes, color protectants, pigments, anti-corrosives, flavors, flavorings, fragrances, polyols, surfactants, electrolytes , organic solvents or silicone derivatives. [171] A sixteenth aspect of the invention relates to a perfume oil which comprises a fragrance or a fragrance mixture according to one of the above embodiments and / or a perfumed product according to the invention.

[172] For applications, it is advantageous for the compounds (I) to (VII) according to the invention, in particular perfume oils (perfume mixtures) containing (II) or (III), to be microencapsulated, spray-dried, as an inclusion complex or as extrusions Use product and add in this form the perfumed (pre-) product.

[173] Another seventeenth aspect of the invention relates to a modified perfume oil comprising a perfume oil according to any one of the preceding embodiments, wherein the perfume oil is microencapsulated, spray dried, as an inclusion complex or as an extrusion product.

[174] The properties of perfume oils modified in this way are further optimized in some cases by so-called "coating" with suitable materials with a view to a more targeted release of fragrance, to which end waxy plastics such as polyvinyl alcohol are preferably used.

[175] The microencapsulation of the perfume oils can be carried out, for example, by the so-called coacervation method with the aid of capsule materials, e.g. made of polyurethane-like substances or soft gelatin. The spray-dried perfume oils can be prepared, for example, by spray-drying a perfume oil-containing emulsion or dispersion, it being possible to use as starches modified starches, proteins, dextrin and vegetable gums.

[176] Inclusion complexes may be e.g. by incorporating dispersions of the perfume oil and cyclodextrins or urea derivatives into a suitable solvent, e.g. Water, to be produced.

[177] Extrusion products can be made by fusing the perfume oils with one suitable waxy substance and by extrusion with subsequent solidification, optionally in a suitable solvent, for example isopropanol, take place.

The compounds (I) to (VII) according to the invention, in particular perfume oils (fragrance mixtures) containing (I), (II) or (III), can be used in concentrated form, in solutions or in another modified form for the preparation from eg Perfumes, perfumes, eau de toilettes, shaving lotions, eau de colognes, pre-shave products, splash colognes and perfumed tea towels, and the perfuming of acidic, alkaline and neutral detergents, e.g. Floor cleaners, window glass cleaners, dishwashing detergents, bath and sanitary cleaners, scouring creams, solid and liquid toilet cleaners, powder and foam carpet cleaners, liquid detergents, powder detergents, laundry pretreatment agents such as bleach, soak and stain removers, fabric softeners, laundry soaps, wash tablets, disinfectants, surface disinfectants and of air fresheners in liquid, gel or applied form, aerosol sprays, waxes and polishes such as furniture polishes, floor waxes, shoe creams and personal care products such as solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving creams, bath oils, oil-in-water, water-in-oil and water-in-oil-in-water type cosmetic emulsions, e.g. Skin creams and lotions, face creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning creams and lotions lotions, hair care products such as Hairsprays, hair gels, hair lotions, hair rinses, permanent and semi-permanent hair dyes, hair styling agents such as cold waving and hair straightening agents, hair lotions, hair creams and lotions, deodorants and antiperspirants such as hair wipes. Underarm sprays, roll-ons, deodorants, deodorants or decorative cosmetics.

[179] A further eighteenth aspect of the invention relates to a perfume oil composition for a shampoo or shower gel comprising a fragrance according to the invention or a perfume mixture and / or a perfumed product according to the invention one of the above inventive aspects or an inventive perfume oil and / or a modified perfume oil according to the aforementioned aspect of the invention, wherein the perfume oil composition further comprises additives suitable for shampoos or shower gels.

A nineteenth aspect of the invention relates to laundry detergent, hygiene product, care product, shampoo or shower gel comprising a perfume or fragrance mixture according to the invention and / or a perfumed product according to one of the above aspects or embodiments and / or a perfume oil according to the invention and / or a modified one according to the invention Perfume oil and / or perfume oil composition.

A further twentieth aspect of the invention relates to the use of a compound according to the invention of the formulas (I) to (VII), in particular according to (I), (II) or (III), as a fragrance or flavor or fragrance or flavor mixture.

A still further twenty-first aspect of the invention relates to the use of a compound of the formulas (I) to (VII) according to the invention, in particular to (I), (II) or (III), for reducing or masking an unpleasant odor and / or for enhancing positive olfactory impressions and / or enhancing flowery and fruity olfactory impressions.

[183] In particular, the invention also relates to the use of one of the following compounds: 2-methyl-1- (4-methyltetrahydropyran-2-yl) propane-1-thiol 7, 2-methyl-1 - [(4R) -4- methyltetrahydropyran-2-yl] propane-1-thiol 8, S- [2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propyl] -ethanethioate 12, 2-methyl-1 - (4 methyltetrahydropyran-2-yl) propane-1-thiol 17. 2-Methyl-1 - [(4S) -4-methyltetrahydropyran-2-yl] propane-1-thiol 18, S- (1-isopropyl-6-methoxy- 4-methyl-hexyl) ethanethioate 19, 8-methoxy-2,6-dimethyl-octane-3-thiol 20, 2-methyl-1- (4-methyl-1,3-dioxan-2-yl) -propane-1 -thiol 21, S- [2-methyl-1- (4-methyl-1,3-dioxan-2-yl) -propyl] ethanethioate 22, 4-methyl-2- (2-methylallyl) -1,3-dioxane 23,3- (4-Methyl-1,3-dioxan-2-yl) butan-2-thiol 24, S- [1- (1,3-dioxan-2-yl) -2-methyl-propyl] ethanethioate 25, 1- (1, 3-dioxan-2-yl) -2-methyl-propane-1-thiol 26, 4-methyl-2- (2-methyl-1-methylsulfanyl- propyl) tetrahydropyran 27, 2- (3,3-dimethylthiiran-2-yl) -4-methyltetrahydropyran 29, for reducing or masking unpleasant taste and / or enhancing positive taste sensations and / or enhancing flowery and fruity taste sensations ,

[Detailed Description of the Invention]

[184] The invention will be described below with reference to exemplary embodiments. As will be explained in more detail below, the compounds of the formula (I) according to the invention can be synthesized in the manner described below. Furthermore, it should be noted that the IUPAC nomenclature may differ from the generic name previously used.

[185] Embodiment 1: Synthesis of S- [2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propyl] ethaneethioate 12 and 2-methyl-1 - [(4R) -4-methyltetrahydropyran -2-yl] propane-1-thiol 8:

[186] Synthesis of S- [2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propyl] ethanethioate 12:

463 g (3.00 mol, 1 .0 eq.) Of (4R) -4-methyl-2- (2-methylprop-1-enyl) tetrahydropyran (L-rose oxide) 11 and 228 g (3.00 mol, 1.10 eq. ) Thioacetic acid are mixed with 2.46 g (15 mmol, 0.005 eq.) Of 2,2-azobis (2-methyl-propionitrile) (AIBN) at 5-10 ° C and then stirred for 30 min at room temperature. The mixture is then slowly heated to 60 ° C and stirred for 10 h at the same temperature until complete conversion. After cooling to room temperature, the reaction solution is subjected directly to a distillative purification (2.0 mbar, 104-1 10 ° C). There are 527.69 g (76% yield, purity 99%) of the desired product S- [2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propyl] -ethanethioat 12 isolated as a diastereomeric mixture of four diastereomers. EI-MS m / z (%): 231 (1, [M] ⁺ ), 215 (1), 187 (1), 173 (1), 154 (4), 139 (4), 99 (100), 81 (15), 69 (12), 55 (12), 43 (42), 29 (4).

Odor description: gum, garlic, sulphurous.

[187] Synthesis of 2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propane-1-thiol 8:

Under nitrogen, 501 g (2.17 mol, 1 .0 eq.) Of S- [2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propyl] -ethanethioate 12 are dissolved in dry methanol (3.3 L) and 300 g (2.17 mol, 1 .0 eq.) Of potassium carbonate. It is then stirred until complete conversion overnight. Then, the reaction mixture is acidified with 1 L of a 2 M hydrochloric acid and treated with 1 L of water and 1 .5 L diethyl ether. The phases are then separated and the resulting aqueous phase extracted with 500 ml_ diethyl ether. The combined organic phases are washed with 500 ml of saturated sodium chloride solution and the phases are separated. The organic phase is dried over sodium sulfate and the solvents are then removed in vacuo. The crude product is purified by distillation (3.6 mbar, 99-102 ° C) and 372 g (91% yield, 99% purity) of 2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propane-1 - Thiol 8 obtained as a mixture of isomers. The composition of the mixture could be determined by GC separation to be 40% 13, 32% 14, 15% 15, 13% 16. The structures of the thus obtained diastereomerically pure compounds could then be elucidated by nuclear magnetic resonance spectroscopy.

EI-MS m / z (%): 188 (1, [M] ⁺ ), 170 (1), 139 (1), 1 1 1 (1), 99 (100), 81 (19), 69 (14 55) (19), 43 (22), 29 (5).

Odor description: strong, fruity, tropical fruit, guava, grapefruit, green, sulfur ig.

Taste description: Passion fruit (25 ppm in 5% sucrose), sulphurous (25 ppm in 0.5% saline).

Compound 13, 14, 15 and 16 are shown as isomers of 8 each from stereochemically different starting compounds. Compounds 13 and 14, and 15 and 16, respectively, are diastereomers that differ by the absolute configuration at C3. Compounds 13 and 14 are C4 (S) -configured and compounds at 15 and 16 are C4 (R) -configured.

13

¹ H-NMR (600MHz, CDCIs, 300K): 0.96 (d, 9-H ₃ ), 0.98 (d, 1 -H ₃ ), 1 .01 (d, 1 '-H ₃ ), 1 .20 (m , 5-H, 7-H), 1 .52 (ddq, 7-H), 1 .60 (m, 6-H, 5'-H), 1 .64 (d, SH), 2.00 (hept. 2-H), 2.63 ("dt", 3-H), 3.34 (ddd, 4-H), 3.41 (ddd, 8-H), 4.02 (ddd, 8'-H) ppm.

3Ji, ₂ = 6.7 Hz, ³ Jr, ₂ = 6.7 Hz, ³ J ₂ , s = 5.2 Hz, ³ J ₃ , SH = 6.8 Hz, ³ J ₃ , 4 = 5.6 Hz, ³ J ₄ , _5i = 1 1 .0 Hz, ³ J, _5c = 2.0 Hz, ³ J ₆ , 9 = 6.3 Hz, ³ Jj, ₈ = 2.2 and 12.5 Hz, ³ J ₇ , v = 4.6 and 1 .6 Hz, ² J ₈ , ₈ ' = 1 1 .4 Hz.

¹³ C-NMR (150 MHz, CDCIs, 300K): 18.20 (1-C), 21 .56 (1'-C), 22.39 (9-C), 30.33 (6- C), 30.89 (2-C), 34.50 (7-C), 38.41 (5-C), 52.79 (3-C), 68.18 (8-C), 79.29 (4-C) ppm.

 14

¹ H-NMR (600MHz, CDCIs, 300K): 0.89 (d, 1-H ₃ ), 0.96 (d, 9-H ₃ ), 0.97 (m, 5-H), 0.98 (d, V-Hs), 1.19 (m, 7-H), 1.24 (d, SH), 1.53 (m, 7'-H), 1.61 (tdd, 6-H), 2.02 (ddt, 5'-H), 2.25 (heptd, 2 -H), 2.75 (dt, 3-H), 3.23 (ddd, 4-H), 3.39 (ddd, 8-H), 4.00 (ddd, 8'-H) ppm.

³ Ji, ₂ = 6.7 Hz, ³ Jr, ₂ = 6.8 Hz, ³ J ₂ , s = 4.5 Hz, ³ J ₃ , SH = 7.8 Hz, ³ J ₃ , 4 = 7.9 Hz, ³ J ₄ , _5i = 11.0 Hz, ³ J, _5c = 2.0 Hz, ³ J ₆ , 9 = 6.5 Hz, ³ J ₇ , ₈ = 2.2 and 12.5 Hz, ³ J ₇ , v = 4.7 and 1.5 Hz, ² J ₈ , ₈ '= 11.3 Hz ,

¹³ C-NMR (150MHz, CDCIs, 300K): 16.79 (1-C), 21.26 (1'-C), 22.40 (9-C), 27.97 (2-C), 30.35 (6-C), 34.64 ( 7-C), 37.66 (5-C), 52.26 (3-C), 68.41 (8-C), 79.21 (4-C) ppm.

 15

¹ H-NMR (600MHz, CDCIs, 300K): 0.88 (d, 1-H ₃ ), 0.99 (d, 1'-H ₃ ), 1.06 (d, 9-H ₃ ), 1.11

(d, SH), 1.26 (m, 7-H), 1.64 (m, 5-H), 1.79 (m, 7'-H), 1.81 (m, 5'-H), 2.02 (m, 6 H),

2.24 (heptd, 2-H), 2.87 (dt, 3-H), 3.53 (td, 4-H), 3.67 (m, 8-H2) ppm.

³ Ji, ₂ = 6.7 Hz, ³ Jr, ₂ = 6.8 Hz, ³ J ₂ , s = 4.1 Hz, ³ J ₃ , SH = 8.2 Hz, ³ J ₃ , 4 = 8.6 Hz, ³ J ₆ , 9 = 7.1

Hz.

¹³ C-NMR (150 MHz, CDCIs, 300K): 16.18 (1-C), 19.10 (9-C), 21.34 (1'-C), 24.82 (6- C), 27.51 (2-C), 32.35 ( 7-C), 34.67 (5-C), 50.43 (3-C), 62.83 (8-C), 74.12 (4-C) ppm.

16

¹ H-NMR (600MHz, CDCIs, 300K): 0.94 (d, 1-Hs), 1.02 (d, 1'-Η ₃ ), 1.08 (d, 9-H ₃ ), 1.27 (m, 7-H) , 1.37 (m, 5-H), 1.66 (d, SH), 1.77 (m, 5'-H), 1.82 (m, 7'-H), 2.07 (m, 6-H), 1.98 (heptd, 2-H), 2.78 (ddd, 3-H), 3.58 (td, 4-H), 3.68 (m, 8-H), 3.78 (m, 8'-H) ppm. ³ Ji, ₂ = 6.7 Hz, ³ Jr, ₂ = 6.8 Hz, ³ J ₂ , s = 4.5 Hz, ³ J ₃ , SH = 6.0 Hz, ³ J ₃ , 4 = 8.6 Hz, ³ J ₄ , _5i = 9.7 Hz, ³ J, _5c = 2.7 Hz, ³ J ₆ , 9 = 7.2 Hz, ³ J ₇ , ₈ = 2.9 and 11.1 Hz, ³ J ₇ , v = 3.5 and 4.8 Hz,

¹³ C-NMR (150MHz, CDCIs, 300K): 17.14 (1-C), 18.46 (9-C), 21.78 (1'-C), 24.92 (6- C), 30.17 (2-C), 31.82 ( 7-C), 35.50 (5-C), 51.81 (3-C), 62.79 (8-C), 74.21 (4-C) ppm.

[188] Embodiment 2

[189] Following the procedure of Example 1, the following mixtures of isomers of 2-methyl-1- (4-methyltetrahydropyran-2-yl) propane-1-thiol 7 were prepared from different Rosenoxid qualities:

[190] Exemplary embodiment 2a: Synthesis of 2-methyl-1- (4-methyltetrahydropyran-2-yl) propane-1-thiol 7:

[191] 2-Methyl-1- (4-methyltetrahydropyran-2-yl) propane-1-thiol 7 was prepared from 4-methyl-2- (2-methylprop-1-enyl) tetrahydropyran (rose oxide) as a mixture of isomers.

 7

 Odor description: fruity, green, sulphurous notes with tropical fruity facets and grapefruit.

[192] Exemplary embodiment 2b: Synthesis of 2-methyl-1- (4-methyltetrahydropyran-2-yl) propane-1-thiol 17:

AND enantiomer

 17

 Following the procedure of Example 1, the following isomer mixture of 2-methyl-1- (4-methyltetrahydropyran-2-yl) propane-1-thiol 17 from 4-methyl-2- (2-methylprop-1-enyl) tetrahydropyran (Rose oxide high ice) of different qualities.

Odor description: green, sulphurous notes with citrus.

[193] Exemplary embodiment 2c: Synthesis of 2-methyl-1 - [(4S) -4-methyltetrahydropyran-2-yl] propane-1-thiol 18:

Following the procedure of Example 1, the following mixture of isomers of 2-methyl-1 - [(4S) -4-methyltetrahydropyran-2-yl] propane-1-thiol 18 from (4S) -4-methyl-2- (2 -methylprop-1-enyl) tetrahydropyran (D-rose oxide) of different qualities. The carbon C6 is configured (S), and C4 is configured to be 70% (R) and 30% (S).

 18

Odor description: strongly fruity, exotic fruity notes and grapefruit. Taste description: flowery (25 ppm in 5% sucrose).

[194] Following the procedure of Example 1, the following thioacetates and thiols were prepared:

[195] Embodiment 2d: Synthesis of S- (1-isopropyl-6-methoxy-4-methylhexyl) ethanethioate 19:

 19

 Following the procedure of Example 1, the thioacetate 19 was prepared.

Odor description: sulphurous, mint, gum.

[196] Embodiment 2e: Synthesis of 8-methoxy-2,6-dimethyl-octane-3-thiol 20:

 20

 Following the procedure of Example 1, the thiol 20 was prepared.

Odor description: Cassis, fruity.

[197] Embodiment 2f: Synthesis of 2-methyl-1- (4-methyl-1,3-dioxan-2-yl) propan-1-thiol 21:

 21

 Following the procedure of Example 1, the Isomerengennisch of thioacetate 21 was prepared.

Odor description: weak, meaty, sulfur.

[198] Embodiment 2g: Synthesis of S- [2-methyl-1- (4-methyl-1,3-dioxan-2-yl) propyl] ethanethioate 22:

22 Following the procedure of Example 1, the Isomerengennisch of thiol 22 was prepared.

Odor description: fruity, rose oxide, rhubarb.

[199] Embodiment 2h: Synthesis of 4-methyl-2- (2-methylallyl) -1,3-dioxane 23:

 23

 Following the procedure of Example 1, the isomer mixture of thioacetate 23 was prepared.

Odor description: Cassis, mint.

[200] Exemplary embodiment 2i: Synthesis of 3- (4-methyl-1,3-dioxan-2-yl) butan-2-thiol 24:

 24

 Following the procedure of Example 1, the isomer mixture of thiol 24 was prepared.

Odor description: fleshy, plastic.

[201] Embodiment 2j: Synthesis of S- [1- (1,3-dioxan-2-yl) -2-methyl-propyl] ethanethioate 25:

 25

 Following the procedure of Example 1, the Isomerengennisch of thioacetate 25 was prepared.

Odor description: fleshy, spicy, sulphurous with facets of onion.

[202] Embodiment 2k: Synthesis of 1- (1,3-dioxan-2-yl) -2-methyl-propane-1-thiol 26:

 26

 Following the procedure of Example 1, the isomer mixture of thiol 26 was prepared.

Odor description: Grapefruit, sulphurous, burned, exotic fruit and onion.

[203] Embodiment 3: Synthesis of 4-methyl-2- (2-methyl-1-methylsulfanyl-propyl) tetrahydropyran 27

 27

To a suspension of 800 mg (20 mmol, 2.0 eq.) Of sodium hydride (60% in mineral oil) in 40 mL of dry THF are added 1.84 g (10.00 mmol, 1 .0 eq.) Of 2-methyl-1 - [( 4R) -4-methyltetrahydropyran-2-yl] propane-1-thiol 8 was added dropwise at room temperature. The mixture is then heated for 30 min to reflux and after cooling to 35 ° C with 1.56 g (1 1 .00 mmol, 1 .1 eq.) Of methyl iodide. The reaction mixture is heated to reflux for a further 120 min. The solution cooled to room temperature is then carefully poured onto 20 ml of ice-water and 20 ml of toluene are added. After phase separation, the aqueous phase is extracted again with 15 ml of toluene. The unified organic phases are dried over sodium sulfate, filtered and freed from the solvents in vacuo. The crude product obtained in this way is purified by Kugelrohr distillation (145-150 ° C, 1 .2 mbar). There are obtained 820 mg (41% yield, 97% purity) of the desired product 4-methyl-2- (2-methyl-1-methylsulfanyl-propyl) tetrahydropyran 27 as a mixture of isomers. Carbon C6 is configured (R), and C4 is configured to be 70% (S) and 30% (R). The configuration at C3 is not defined.

Odor description: spicy, garlic, pungent, green.

EI-MS m / z (%): 202 (10, [M] ⁺ ), 154 (1), 139 (2), 99 (100), 81 (20), 69 (16), 55 (19) 43 (40), 29 (6). Following the procedure of Example 3, the following ether is synthesized: [204] Embodiment 4: Synthesis of 8-methoxy-2,6-dimethyl-oct-2-ene 28:

 Following Example 14, 15.63 g (0.1 mol, 1 .0 eq.) Of citronellol are dissolved in 200 ml of THF and mixed with 4.80 g (0.12 mol, 1 .2 eq.) Of sodium hydride (60% in mineral oil) and 17.03 g ( 0.12 mol, 1 .2 eq.) Of methyl iodide. There are obtained 4.1 g (20% yield, 85% purity) of 8-methoxy-2,6-dimethyl-oct-2-ene 28, which were used without distillation in the subsequent stage.

[205] Embodiment 5a: Synthesis of 2- (3,3-dimethyloxiran-2-yl) -4-methyltetrahydropyran 30:

 30

1 15.7 g (750 mmol, 1 .00 eq.) Of 4-methyl-2- (2-methylprop-1-enyl) tetrahydropyran (rose oxide) are dissolved in 1.5 L of dichloromethane and cooled to 0 ° C. Then 207.1 g (900 mmol, 1 .20 eq.) Of mefa-chloroperbenzoic acid are added in portions within 3.5 hours and stirred for 20 min at the same temperature. It is then warmed to room temperature and stirred for 2 hours until complete conversion. The reaction mixture is then added carefully at 10 ° C with 2L of a 15% sodium hydroxide solution and diluted with 1 L dichloromethane. The phases are shaken and separated. The organic phase is dried over sodium sulfate, filtered and the solvents are removed in vacuo. The crude product of 2- (3,3-dimethyloxiran-2-yl) -4-methyl-tetrahydropyran 30 obtained in this way (125.0 g, 99% purity, 97% yield) is used directly in the subsequent reaction.

[206] Embodiment 5b: Synthesis of 2- (3,3-dimethylthiiran-2-yl) -4-methyltetrahydropyran 29:

 29

 42.6 g (250 mmol, 1 .00 eq.) 2- (3,3-Dimethyloxiran-2-yl) -4-methyl-tetrahydropyran 30 are dissolved in 125 ml of isopropanol and treated at room temperature with 19.0 g (250 mmol, 1. 00 eq.) Of ammonium thiocyanate and 13.8 g (25 mmol, 0.10 eq.) Of cerium (IV) ammonium nitrate. The reaction mixture is stirred for 48 hours at room temperature until no reaction progress can be detected. The batch is then filtered and the filtrate is concentrated. The residue is taken up in 70 ml of tert-butyl methyl ether. The precipitated urea is filtered off again and the organics dried over sodium sulfate. After removal of the solvent, 20 g of crude product are obtained, which is purified by distillation (0.4 mbar, b.p .: 40 ° C) and by flash chromatography (cyclohexane / ethyl acetate). There are obtained 1.89 g (10 mmol, 4% yield) of 2- (3,3-dimethylthiiran-2-yl) -4-methyl-tetrahydropyran 29 as a colorless liquid. Compound 29 is obtained as a mixture of cis-29 / trans-29 = 5: 1.

Odor description isomer mixture: rose, gum, green. AND enantiomer

 z 9

 cis-29

EI-MS m / z (%): 186 (9, [M] ⁺ ), 171 (1), 153 (57), 139 (5), 99 (100), 81 (27), 69 (24), 55 (28), 43 (54), 29 (11).

¹ H-NMR (400MHz, CDCIs, 300K): 0.97 (d, 9-H ₃ ), 1.25 (m, 5-H ₂ ), 1.55 (m, 6.7-Hs), 1.61 (s, 1-Hs ), 1.63 (s, 1'-H ₃ ), 2.72 (d, 3-H), 3.04 (ddd, 4-H), 3.39 (m, 8-H), 4.00 (ddd, 8'-H) ppm ,

³ Js, 4 = 9.1 Hz, ³ J ₄ , ₅ = 11.1 Hz, ³ J, ₅ '= 2.1 Hz, ³ J ₆ , 9 = 6.4 Hz, ³ J ₇ , 8 = 4.6 Hz, ³ J ₇ ', 8 = 1.4

¹³ C-NMR (100MHz, CDCIs, 300K): 22.24 (9-C), 23.02 (1-C), 30.14 (6-C), 30.57 (1'-C), 34.39 (7-C), 39.60 ( 5-C), 47.58 (2-C), 51.13 (3-C), 68.24 (8-C), 79.04 (4-C) ppm.

AND enantiomer

 trans-29

EI-MS m / z (%): 186 (5, [M] ⁺ ), 171 (1), 153 (32), 139 (5), 99 (100), 81 (24), 69 (19), 55 (27), 43 (49), 29 (11).

¹ H-NMR (400MHz, CDCIs, 300K): 1.05 (d, 9-H ₃ ), 1.25 (m, 5-H), 1.62 (m, 1-Hs), 1.64 (s, 1-Hs), 1.81 (m, 5.7-Hs), 2.12 (dtd, 6-H), 2.88 (d, 3-H), 3.45 (m, 4-H), 3.68 (ddd, 8-H), 3.79 (dt, 8'-H) ppm. ³ Js, 4 = 9.4 Hz, ³ J ₆ , 9 = 7.1 Hz, ³ J ₇ , 8 = 9.5 Hz, ³ J ₇ ', 8 = 3.1 Hz, ² J ₈ , 8 * = 1 1 .9 Hz, ³ J ₇ , 8 '= 4.7 Hz.

¹³ C-NMR (100MHz, CDCIs, 300K): 18.93 (9-C), 23.03 (1-C), 24.88 (6-C), 30.67 (1'-C), 32.25 (7-C), 36.64 ( 5-C), 47.88 (2-C), 50.10 (3-C), 62.75 (8-C), 74.02 (4-C) ppm.

[207] Embodiment 6: Synthesis of 4-methyl-2 - [(E) -1-methylprop-1-enyl] -1,3-dioxane 31:

 31

 21 .03 g (0.25 mol, 1 .0 eq.) Of (E) -2-methylbut-2-enal, 47.31 g (0.53 mol, 2.1 eq.) Of 1,3-butanediol and 1 .00 g (5.8 mmol, 0.02 eq.) Of para-toluenesulfonic acid are dissolved in 250 ml of toluene and heated to reflux on a water separator for 5 h. The reaction mixture is then neutralized with 50 ml of a saturated sodium bicarbonate solution and the phases are subsequently separated. The organic phase is washed three times with 40 ml_ water and dried over sodium sulfate. After phase separation, the organic phase solvents are removed in vacuo. The residue is purified by Kugelrohr distillation (94 ° C., 1 .1 mbar). There are obtained 15.8 g (37% yield, 93% purity) of a binary isomer mixture of 4-methyl-2 - [(E) -1-methylprop-1-enyl] -1,3-dioxane 31 (trans-31 / cis -31 = 7: 1). The mixture was used directly.

 trans-31

EI-MS m / z (%): 156 (3, [M] ⁺ ), 141 (62), 101 (14), 87 (21), 84 (28), 69 (28), 55 (100), 41 (17), 29 (17).

¹ H-NMR (400MHz, CDCIs, 300K): 1.25 (d, 9-H _3), 1:43 (m, 7-H), 1.64 (dq, 1-H _3), 1.67 (m, 7-H ') , 1.69 (m, 4-H ₃ ), 3.81 (m, 6,8-H ₂ ), 4.13 (ddd, 8'-H), 4.82 (s, 5-H), 5.71 (ddd, 2-H) ppm.

³ Ji, ₂ = 6.8 Hz, ³ J ₆ , 9 = 6.2 Hz, ³ J ₇ , 8 = 5.0 Hz, ³ Jr, ₈ = 1.5 Hz, ² J ₈ , 8 '= 11.5 Hz.

¹³ C-NMR (100MHz, CDCIs, 300K): 13.09 (1-C), 17.78 (4-C), 21.87 (9-C), 33.03 (7-C), 66.67 (8-C), 72.87 (6 -C), 98.54 (5-C), 124.52 (2-C), 133.65 (3-C) ppm.

 cis-31

EI-MS m / z (%): 156 (6, [M] ⁺ ), 141 (66), 101 (19), 87 (21), 84 (24), 69 (28), 55 (100), 41 (17), 29 (17).

¹ H-NMR (400MHz, CDCIs, 300K): 1.25 (d, 9-H ₃ ), 1.43 (m, 7-H), 1.61 (d, 1-Hs), 1.67 (m, 7-H '), 1.75 (m, 4-H ₃ ), 3.81 (m, 6.8-H ₂ ), 4.13 (m, 8'-H), 5.32 (s, 5-H), 5.45 (m, 2-H) ppm ,

¹³ C-NMR (100MHz, CDCIs, 300K): 11.10 (4-C), 12.94 (1-C), 21.82 (3-C), 33.01 (7-C), 66.63 (8-C), 72.87 (6 -C), 104.67 (5-C), 123.76 (2-C), 133.81 (3-C) ppm.

[208] Embodiment 7a: Synthesis of 2- (2-methylprop-1-enyl) -1,3-dioxane 32:

 32

 Following the procedure of Example 6, this acetal 32 was synthesized.

[209] Embodiment 7b: Synthesis of 4-methyl-2- (2-methylprop-1-enyl) -1,3-dioxane 33:

 33

Following the procedure of Example 6, this acetal 33 was synthesized.

[210] Table 1: Overview of the new fragrances and their perfumery characterization:

27 würzig, Knoblauch, grün

27 spicy, garlic, green

f 21 weak, fleshy, sulfur

g 22 fruity, floral, rhubarb

h 23 Cassis, mint

fleischig, würzig, schwefelig mitj 25 i 24 meaty, Gunnnni

fleshy, spicy, sulphurous mitj 25

 Facets of onion.

Grapefruit, sulphurous, burnt, k 26

2e 20 Cassis, fruchtig exotic fruit and onion d 19 sulphurous, fruity, mint, gum

2e 20 Cassis, fruity

5 29 Floral, rose, gum, green

[211] Embodiment 8: Perfume Composition I

 The following perfume oil can be used to perfume shampoos and shower gels.

[212] Table 2:

DAMASCENON TOTAL 1 ,5

DAMASCENON TOTAL 1, 5

DAMASCON ALPHA 2

DAMASCONE DELTA 1

DECALACTON GAMMA 20

DIHYDROMYRCENOL 35

DIMETHYLBENZYLCARBINYLBUTYRATE 25

ETHYL ACETATE 1

ETHYLBUTYRATE 1

FLORAZON 1

FLOROSA 8

GERANIOL SUPRA 1

GERANYLACETATE PUR 13

GLOBALIDE® 30

HEDION 5

HERBAFLORAT 23.5

HEXENAL TRANS-2 10% DPG 3

HEXENOL CIS-3 2.5

H EXE NYLAC ETAT CIS-3 3,5

HEXENYLBENZOATE CIS-3 4

HEXENYLPROPIONATE CIS-3 0,6

HEXYLACETATE 10

HEXYLISOBUTYRATE 6.5

HEXYL SALICYLATE 30

HEXYLZIMTALDEHYDE ALPHA 67

IONON BETA 25.5

ISOAMYL ACETATE 1, 4

ISOAMYL ALCOHOL 10% DPG 2

ISOAMYLBUTYRATE 6.5

JASMAPRUNAT 16

LEAFOVERT® 0.5

LINALOOL 19

LINALOOL OXIDE 10% DPG 2

MANZANATE 5.5 NEOFOLIONE 0.8

 PHENIRAT® 70

 PHENYLETHYLBUTYRATE 10% DPG 1, 5

 PHENYLETHYL ISOBUTYRATE 16

 PRENYLACETATE 2.5

 TAMARINE TYPE BASE 6

 UNDECAVERTOL 7

 VERTOCITRAL 6.5

 FRAMBINON® 10% DPG 2

 HEXENOL CIS-3 10% DPG 10

[213] The produced perfume oil was divided into two equal parts. To exclude dilution effects, a first portion of the perfume oil was added with 0.4% by weight of dipropylene glycol (DPG), based on the total amount of the first part of the perfume oil. The second part of the perfume oil was admixed with 0.4% by weight of 2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propane-1-thiol 8 1% DPG (ie a 1% solution from compound 8 in DPG) based on the total amount of the perfume oil portion. The resulting compositions were compared olfactorily.

[214] The addition of 0.4% by weight of 2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propane-1-thiol 8 1% DPG gives the composition a surprisingly strong, vibrating fruitiness. The fresh and juicy aspects of the composition are emphasized, giving the composition more expression of elegance.

[215] Exemplary embodiment 9: perfume oil composition II

 The following perfume oil can be used to perfume shampoos and shower gels.

[216] Table 3:

ALDEHYD C14 SOG 10% DPG 2

ALDEHYD C14 SOG 10% DPG 2

ALDEHYDE C18 SOG. 10% DPG 4

ALLYLCAPRONATE 10% DPG 3

AMBERWOOD® F 15

ANETHOL SUPRA 1

BERGAMOT IDENTOIL® 150

BUCCOXIME® 1% DPG 18

CANTHOXAL 20

CITRONENOEL ITAL. 5

DAMASCENON TOTAL 10% DPG 6

DAMASCONE DELTA 10% DPG 5

DEWFRUIT TYPE BASE 25

ETHYLENE BRASSYLATE 75

ETHYL LINENOLOOL 38

ETHYLMALTOL 20

ETHYLVANILLINE 30

GERANYLACETATE 60 1

GLOBALIDE® 60

GLOBANONE® 20

GUAJYLACETATE 5

HEDION 145

H EXE N YLSAL I CYLATE CIS-3 13

HEXYLACETATE 10% DPG 3

IONON BETA 20

IRON ALPHA 1

IRONAL 1

ISO E SUPER 1 15

ISORALDEIN 70 12

LIMETTE OIL TERPENE 5

LINALOOL 5

MENTHA ARV. OEL DMO 10% DPG 5

PATCHOULIOEL DELETE DM 1, 5 PRUNELLA TYPE BASE 6

 SANDALWOOD MYSORE TYPE BASE REPL. 1

 STYROLYL ACETATE 2

 SULFURROL 1

 TERRANOL® 10% DPG 10

 VANILLIN 25

 VERTOCITRAL 1, 5

 YSAMBER® K 12

[217] The produced perfume oil was divided into two equal parts. To exclude dilution effects, a first portion of the perfume oil was admixed with 4% by weight of dipropylene glycol (DPG), based on the total amount of the first portion of the perfume oil. The second part of the perfume oil was mixed with 4% by weight of 2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propane-1-thiol 8 1% DPG (ie a 1% solution of compound 8 in DPG), based on the total amount of the part of the perfume oil. The resulting compositions were compared olfactorily.

[218] The addition of 4% by weight of 2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propane-1-thiol 8 1% DPG gives the composition a strong playful fruitiness. In detail, sun-kissed exotic notes harmonize with sparkling aspects of grapefruit. The powdery note of black currant also gives the composition more fullness.

[219] Embodiment 10: Perfume Oil Composition III

 The following perfume oil can be used to perfume shampoos, shower gels and air care products.

[220] Table 4:

ALKOHOL C 6 KOSCHER 140

ALCOHOL C 6 KOSHER 140

 APRIFLOREN® 30

 BENZYL BENZOATE M 168

 CALONE 10

 DIMETHYLBENZYLCARBINYLBUTYRATE 40

 DIMETHYL SULFIDE 10% BB 10

 DIPHENYL OXIDE 30

 ETHYLMALTOL 2

 ETHYLVANILLINE 10% BB 20

 FURANEOL 25

 HELIONAL 80

 HERBYLPROPIONATE 10

 HEXENOL CIS-3 90

 HEXENYLPROPIONATE CIS-3 60

 METHYLPHENYL ACETATE 10% BB 5

 NEROL 900 30

 NONALACTON DELTA 20

 ORANGE OIL 100

 PENTANDION-2,3 10% BB 5

 THIOMENTHANONE-8,3 10% BB 10

 TROPICOL 0.1% IPM 25

[221] The produced perfume oil was divided into two equal parts. In order to exclude dilution effects, a first part of the perfume oil was admixed with 2% by weight of dipropylene glycol (DPG), based on the total amount of the first part of the perfume oil. The second part of the perfume oil was admixed with 2% by weight of 2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propane-1-thiol 8 1% DPG, based on the total amount of the part of the perfume oil , The resulting compositions were compared olfactorily.

[222] The addition of 2% by weight of 2-methyl-1 - [(4R) -4-methyltetrahydropyran-2-yl] propane-1-thiol 8 1% DPG gives the composition the impression of a fleshy yellow mango with aspects of naturally green mango skin and its fibers. Overall, the composition is characterized by more velvety volume.

Claims

claims 1 . Compounds of the formula (I)

 in which,  X represents an oxygen atom or a methylene group, R ^{1 represents} a hydrogen atom or a linear or branched alkyl radical having 1 to 8 carbon atoms, preferably a methyl group, R ^{2 represents} a hydrogen atom or a linear or branched alkyl radical having 1-8 carbon atoms, preferably a hydrogen atom, R ^{3 represents} a linear or branched alkyl radical having 1-8 carbon atoms, preferably a methyl group, R ^{4 represents} a hydrogen atom or a linear or branched alkyl radical having 1-8 carbon atoms, preferably a methyl group, R ^{5 represents} a linear or branched alkyl radical having 1-8 carbon atoms, preferably a methyl group, or R ^{5 is} omitted, Y represents a hydrogen atom, a linear or branched alkyl radical having 1-8 carbon atoms or an acetyl group, or Y is omitted, wherein there is no bond or a single bond at the location of a dashed line between Oa atom and Cf atom, wherein in the presence of a single bond in formula (I) the group R ^{5 is} omitted, wherein at the location of one of the dashed lines between S atom and Cg-atom or between S-atom and Ch-atom respectively no bond or a single bond is present, with the proviso that at least one of the dashed bonds is present as a single bond, wherein in the presence of a single bond between S-atom and the C Atoms C _g and Ch in formula (I) the group Y is omitted. 2. Compounds of the formula (II)

 in which  X represents an oxygen atom or a methylene group, R ^{1 represents} a hydrogen atom or a linear or branched alkyl radical having 1 to 8 carbon atoms, preferably a methyl group, R ^{2 represents} a hydrogen atom or a linear or branched alkyl radical having 1-8 carbon atoms, preferably a hydrogen atom, R ^{3 represents} a linear or branched alkyl radical having 1-8 carbon atoms, preferably a methyl group, R ^{4 represents} a hydrogen atom or a linear or branched alkyl radical having 1-8 carbon atoms, preferably a methyl group, Y represents a hydrogen atom, a linear or branched alkyl radical having 1-8 carbon atoms or an acetyl group, or Y is omitted, wherein at the location of one of the dashed lines between S atom and Cg atom or between S atom and Ch atom each bond or a single bond is present, with the proviso that at least one of the dashed bonds is present as a single bond, wherein Presence of one single bond between the S atom and the C atoms C _g and Ch in formula (II) the group Y is omitted. 3. Compounds of the formula (III)

 in which,  X represents an oxygen atom or a methylene group, R ^{1 represents} a hydrogen atom or a linear or branched alkyl radical having 1 to 8 carbon atoms, preferably a methyl group, R ^{2 represents} a hydrogen atom or a linear or branched alkyl radical having 1-8 carbon atoms, preferably a hydrogen atom, R ^{3 represents} a linear or branched alkyl radical having 1-8 carbon atoms, preferably a methyl group, R ^{4 represents} a hydrogen atom or a linear or branched alkyl radical having 1-8 carbon atoms, preferably a methyl group, R ^{5 represents} a linear or branched alkyl radical having 1-8 carbon atoms, preferably a methyl group, Y represents a hydrogen atom, a linear or branched alkyl radical having 1-8 carbon atoms, or Y is omitted, wherein at the location of one of the dashed lines between S atom and Cg atom or between S atom and Ch atom each no bond or a single bond is present, with the proviso that at least one of the dashed bonds is present as a single bond, wherein in the presence of a single bond between the S atom and the C atoms C _g and Ch in formula (III) the group Y is omitted. 4. Compounds according to one of the preceding claims, wherein the compounds in the form of a position isomer mixture of the two compound variants each having a single bond of the carbon atoms C _g or Ch to the S atom. 5. Compounds according to any one of the preceding claims wherein the compounds are in the form of a diastereomeric mixture having stereocenters at two or more of the positions selected from the group consisting of: Cd, Cf, _Cg , Ch. 6. Compounds according to any one of claims 1, 2, 4 or 5, wherein the compounds are present at the position Cd (R) -configured. 7. Compounds according to one of the preceding claims, wherein the compounds in the position Cd (R) -configured and in the position Cf (S) - configured. Compounds according to any one of the preceding claims wherein the compounds are in the form of a cis: trans isomeric mixture at positions Cd: Cf, of predominant cis configuration. Process for the preparation of a compound (I), (II) or (III) according to any preceding claim comprising at least the steps (i), (ii) and characterized in that the corresponding starting material of the formula (IV)

(i) is reacted with thioacetic acid, preferably with free-radical catalysis, in order to obtain, with a regioselectivity of greater than or equal to 95%, the compound of the formula (V):

(ii) optionally subsequently cleaving off the acetyl group to obtain the following compound of formula (VI):

(iii) and optionally thereafter alkylating the thiol group to obtain the compounds (I), (II) or (III), wherein the groups X, Y, R ¹ , R ² , R ³ , R ⁴ and R ⁵ and the dashed lines each have the meaning given in claim 1. Process for the preparation of a compound (I), (II) or (III) according to one of the preceding claims 1 to 8, comprising at least steps (i) and (ii), characterized in that the double bond of the corresponding starting material of the formula (IV ):

(i) is epoxidized with a peracid, preferably with mefa-chloroperbenzoic acid, (ii) and then reacting the oxirane formed under (i), preferably with ammonium thiocyanate, to give the thiirane of the formula (VII) below:

where the groups X, Y, R ¹ , R ² , R ³ , R ⁴ and R ⁵ and the dashed lines each have the meaning given in claim 1. 1 1. A fragrance or flavoring agent comprising a compound of the formulas (I) to (VII) according to any one of the preceding claims. 12. fragrance or flavor mixture with a fragrance or flavor according to the preceding claim further comprising one or more additional fragrances and / or flavorings, wherein the additional or one, more or all fragrances and / or flavorings is selected from the group consisting of: extracts from natural raw materials, preferably essential oils, concretes, absolues, resines, resinoids, balsams, tinctures and / or individual fragrances, preferably from the group of hydrocarbons, aliphatic alcohols, aliphatic aldehydes and their acetals, aliphatic Ketones and their oximes, aliphatic sulfur compounds, aliphatic nitriles, esters of aliphatic carboxylic acids, acyclic terpene alcohols, acyclic terpene aldehydes and ketones, cyclic terpene alcohols, cyclic terpene aldehydes and ketones, cyclic alcohols, cycloaliphatic alcohol le, the cyclic and cycloaliphatic ethers, the cyclic and macrocyclic ketones, the cycloaliphatic aldehydes, the cycloaliphatic ketones, the esters of cyclic alcohols, the esters of cycloaliphatic alcohols, the araliphatic alcohols, the esters of araliphatic alcohols and aliphatic carboxylic acids, the araliphatic ethers, the aromatic and araliphatic Aldehydes, aromatic and araliphatic ketones, aromatic and araliphatic carboxylic acids and their esters, nitrogen-containing aromatic compounds, phenols, phenyl ethers and phenyl esters, heterocyclic compounds, and lactones. 13. fragrance or flavor mixture according to the preceding claim, wherein the total amount of compounds (I) to (VII) based on the total weight of the fragrance or flavor mixture 0.00001 to 5 wt .-%, preferably 0.00001 to 1 wt .-%, and particularly preferably 0.0005 to 0.01 wt .-%, is. A perfumed product comprising a fragrance or fragrance mixture according to any of claims 1-1 and an adjunct, preferably a carrier, said excipient comprising one or more substances selected from the group consisting of: porous inorganic materials such as, preferably, light sulphate, silica gels , Zeolites, gypsum, clays, clay granules, aerated concrete or organic materials such as preferably wood, cellulose-based substances, sugars or plastics such as preferably PVC, polyvinyl acetates or polyurethanes. A perfumed product comprising a fragrance or fragrance mixture according to any of claims 1-13 or the perfumed product according to the preceding claim further comprising one or more additives selected from the group consisting of preservatives, abrasives, anti-acne agents, anti-aging agents , anti-bacterial, anti-cellulite, anti-dandruff, anti-inflammatory, anti-irritant, anti-irritant, antimicrobial, antioxidant, astringent, antiperspirant, antiseptic, antistatic, binder, buffer, carrier, chelating, cell stimulants, cleansing, nourishing Agents, depilatory agents, surfactants, deodorants, antiperspirants, emollients, emulsifiers, enzymes, essential oils, fibers, film formers, fixatives, foaming agents, foam stabilizers, foaming inhibitors, foam boosters, fung izide, gelling agents, gelling agents, hair care products, hair styling agents, hair relaxants, moisturizers, moisturizers, moisturizers, bleaches, tonic, stain removers, optically brighteners, antifoaming agents, antisoiling agents, anti-friction agents, lubricants, moisturizers, ointments, opacifiers , plasticizers, masks, polishes, brighteners, polymers, powders, proteins, moisturizers, abrasives, silicones, skin soothers, skin cleansers, skin care agents, skin-healing agents, skin-whitening agents, skin-protecting agents, skin softeners, cooling agents, skin-cooling agents , warming agents, skin warming agents, stabilizers, UV-absorbing agents, UV filters, detergents, fabric softeners, suspending agents, skin tanning agents, thickeners, vitamins, oils, waxes, fats, phospholipids, sown saturated fatty acids, mono- or polyunsaturated fatty acids, α-hydroxy acids, polyhydroxy fatty acids, plasticizers, dyes, color protectants, pigments, anti-corrosives, flavors, flavorings, fragrances, polyols, surfactants, electrolytes, organic solvents or silicone derivatives. 16. perfume oil comprising a fragrance or a fragrance mixture according to any one of claims 1 1 to 13 and / or a perfumed product according to any one of claims 14 or 15. A modified perfume oil comprising a perfume oil according to the preceding claim, wherein the perfume oil is microencapsulated, spray-dried, as an inclusion complex or as an extrusion product. 18. perfume oil composition for a shampoo or shower gel comprising a fragrance or a fragrance mixture according to any one of claims 1 1 to 13 and / or a perfumed product according to any one of claims 14 or 15 or a perfume oil according to claim 16 and / or a modified perfume oil according to claim 17 wherein the perfume oil composition further comprises additives suitable for shampoos or shower gels. 19, detergent, hygiene product, care product, shampoo or shower gel comprising a fragrance or a fragrance mixture according to any one of claims 1 1 to 13 and / or a perfumed product according to any one of claims 14 or 15 and / or a perfume oil according to claim 16 and / or a Modified perfume oil according to claim 17 and / or a perfume oil composition according to claim 18. 20. Use of a compound of formulas (I) to (VII) according to any one of the preceding claims as olfactory or flavor or fragrance or flavor mixture. 21. Use of a compound of formulas (I) to (VII) according to any one of the preceding claims for reducing or masking unpleasant odor and / or enhancing positive odor sensations and / or enhancing flowery and fruity odor sensations.