Precursors for controlled release of alpha, beta-unsaturated aldehydes or ketones and other highly impact aromatic substances

Abstract

The present invention relates generally to compounds of formula (I) as defined herein. The present invention also relates to aromatic substance mixtures as defined herein and methods for their production, and also to flavor products as defined herein and methods for their production. The invention also relates to the use of a compound of formula (I) as defined herein as a precursor for the release of two or more different pleasant odors of aromatics, to a method for the release of two or more different pleasant odors of aromatics, and to a thiol as defined herein.

Description

Technical Field

[0001] The present invention mainly relates to compounds of formula (I) as defined herein. The present invention also relates to a mixture of aromatic substances as defined herein and a method for producing the same, and also relates to a fragrance product as defined herein and a method for producing the same. The present invention also relates to the use of compounds of formula (I) as defined herein as a precursor for releasing two or more aromatic substances with different pleasant odors, and also relates to a method for releasing two or more aromatic substances with different pleasant odors, and also relates to thiols as defined herein.

[0002] Further aspects and preferred embodiments of the invention are apparent from the following description, the accompanying examples and especially the accompanying patent claims. Background Art

[0003] In the fragrance industry, there is a particular interest in the controlled and sustained release of certain fragrances, especially those with high volatility or low substantiality. For example, in the field of textile washing, it is highly desirable that the pleasant smell of fragrance substances or essential oils used in detergents or fabric softeners be felt on clothing for a long time after the textiles have been washed and dried.

[0004] Precursors are known in the fragrance industry, for example from α,β-unsaturated carbonyl compounds and thiols by Michael addition. They usually release a pleasant smelling α,β-unsaturated carbonyl compound, such as an α,β-unsaturated aldehyde or ketone. This release takes place in a controlled manner so that highly volatile aroma substances can be perceived by the senses, which would not be achieved if the aldehyde or ketone compounds were used directly in the essential oil.

[0005] The fragrance industry is in urgent need of precursors that can release several fragrance substances simultaneously or over time. This will expand the scenting options of fragrances. In addition, there is a particularly high demand for fragrance substances that have a strong olfactory effect even at low doses (i.e., low odor thresholds), so-called "high-impact" fragrance substances.

[0006] The currently known precursors are limited to releasing α, β-unsaturated carbonyl compounds with fragrance. However, since common, especially short-chain thiol compounds give people an unpleasant odor impression, the prior art teaches the use of thiol compounds that are as odorless as possible to form precursors. For example, in patent application WO 2004 / 105713 A1, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane are reacted with α, β-unsaturated carbonyl compounds to form precursors. In the method taught therein, only the released α, β-unsaturated carbonyl compounds are used as aromatic substances.

[0007] In patent application WO 2015 / 032885 A1, short-chain thiol compounds are used to form precursors. Also in this patent document, only α, β-unsaturated carbonyl compounds released from the precursors are used as aromatic substances. It is described that, although short-chain thiol compounds with an unpleasant odor are also released from the precursors, surprisingly, this does not have a significant negative impact on the positive olfactory effect of the α, β-unsaturated carbonyl compounds, so that overall, unexpectedly, the positive olfactory impression of the released α, β-unsaturated carbonyl compounds dominates. Summary of the invention

[0008] The main object is to provide an improved precursor of a high impact fragrance that meets the above requirements, i.e. can release a pleasant odor in a controlled manner for a long time. Such release should preferably be possible from surfaces treated with the precursor, in particular from textiles.

[0009] Surprisingly, this object is achieved by compounds of the formula (I)

[0010]

[0011] (i) wherein R is selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues, alkenyl residues or dienyl residues, preferably, wherein the residue also carries one, two, three, four or more C1 to C4 linear, cyclic or branched alkyl substituents, alkenyl substituents or dienyl substituents (and wherein the substituents may be the same or different from each other), and

[0012] wherein R' is selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues, alkenyl residues or dienyl residues, preferably, wherein the residue also carries one, two, three, four or more C1 to C4 linear, cyclic or branched alkyl substituents, alkenyl substituents or dienyl substituents (and wherein the substituents may be the same or different from each other), and

[0013] Where R 1 Selected from hydrogen and C1 to C 10, preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues, alkenyl residues or dienyl residues, preferably, wherein the residue also carries one, two, three, four or more C1 to C4 linear, cyclic or branched alkyl substituents, alkenyl substituents or dienyl substituents (and wherein the substituents may be the same or different from each other), and

[0014] Where R 2 Choose from C4 to C 15 , preferably C4 to C 12 , more preferably C5 to C 12 , more preferably C6 to C 12 , more preferably C7 to C 12 , most preferably C8 to C 12 The group consisting of a linear, cyclic or branched alkyl residue of , preferably further comprising one, two or more functional groups selected from the group consisting of ethers, alcohols and ketones, more preferably further comprising one ether group, or two ether groups, or one alcohol group, or one ketone group, and

[0015] Where R 3 Selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues, alkenyl residues or dienyl residues, preferably, wherein the residue also carries one, two, three, four or more C1 to C4 linear, cyclic or branched alkyl substituents, alkenyl substituents or dienyl substituents (and wherein the substituents may be identical to or different from each other);

[0016] or

[0017] (ii) where R', R 2 and R 3 are independently selected from the groups defined in (i), and R and R 1 bonded together to form a saturated or unsaturated ring system containing 5 to 10 carbon atoms, preferably containing 6 to 8 carbon atoms, most preferably containing 6 carbon atoms, preferably, wherein the ring system also carries one, two, three, four or more C1 to C5 linear, branched or cyclic alkyl substituents, alkenyl substituents or dienyl substituents (and wherein the substituents may be the same or different from each other);

[0018] or

[0019] (iii) where R', R 1 and R 2 are independently selected from the groups defined in (i), and R and R3 bonded together to form a saturated or unsaturated monocyclic or bicyclic ring system containing 5 to 10 carbon atoms and optionally 1 or 2 ether functions, preferably containing 6 to 8 carbon atoms and optionally 1 ether function, most preferably containing 6 carbon atoms, preferably, wherein the ring system also carries one, two, three, four or more C1 to C5 straight-chain, branched or cyclic alkyl substituents, alkenyl substituents or dienyl substituents, preferably carrying one, two or more methyl groups.

[0020] The ring system defined in (ii) above includes 1 The carbon atom bonded to the ring system (iii) above includes the rings R and R 3 Bonded carbon atoms.

[0021] The compounds of formula (I) (ie the precursors) may be in the form of pure diastereomers or stereoisomers, or in the form of any mixture of said isomers.

[0022] The compounds of formula (I) as defined herein were previously unknown in the flavor industry. Therefore, the suitability of the compounds of formula (I) as precursors for releasing aromatic substances was previously unknown. In the process of basic research constituting the present application, contrary to the teaching in the prior art that the released thiol compounds have negative olfactory effects, it was surprisingly found that the compounds of formula (I) according to the present invention can release both α, β-unsaturated aldehydes or ketones with pleasant odors (high impact), and thiol compounds with pleasant odors (high impact). The release of the two (or more) different aromatic substances and the sensory perception brought about thereby are advantageously carried out in a controlled manner, preferably at different time points, which is particularly surprising. For example, the sensory odor impression of the released thiol compounds (such as sulfur fruity notes) can be strongly perceived on wet clothes, especially on clothes just washed, while the released α, β-unsaturated aldehydes or ketones provide a lasting, fresh odor impression (e.g., fresh, grassy green and / or floral notes) on dry clothes.

[0023] Other advantages of the present invention are:

[0024] Due to the controlled release of two different high-impact aromatic substances (α,β-unsaturated aldehyde or ketone compounds, thiol compounds) with low odor thresholds and pleasant odors, a clear odor perception occurs when even small amounts of the compounds of formula (I) according to the invention are used.

[0025] Compared to the precursors of the prior art, the present invention achieves a higher atom economy, since surprisingly both compounds (α,β-unsaturated aldehyde or ketone compound, thiol compound) released from the compounds of formula (I) according to the present invention contribute to the generation of a pleasant odor profile.

[0026] - The positive effect of the compounds of formula (I) according to the invention on the odor impression is achieved both on wet laundry (thiol compounds) and on dry laundry (α,β-unsaturated aldehyde or ketone compounds), since different aromatic substances are preferably released from the compounds of formula (I) according to the invention and / or are perceived by the senses at different points in time.

[0027] The thiol compound released by the compound of formula (I) according to the invention not only improves the fragrance retention and / or deposition of the compound of formula (I) according to the invention on, for example, textiles, hair or skin, but also acts as a pleasant-smelling fragrance substance itself.

[0028] According to a preferred embodiment of the compound of formula (I) of the present invention,

[0029] R is selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues or alkenyl residues, preferably wherein the residues also carry one, two, three, four or more C1 to C4 linear, cyclic or branched alkyl substituents, alkenyl substituents or diene substituents (and wherein the substituents may be identical to or different from each other), and

[0030] R' is selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues or alkenyl residues, preferably wherein the residues also carry one, two, three, four or more C1 to C4 linear, cyclic or branched alkyl substituents, alkenyl substituents or diene substituents (and wherein the substituents may be identical to or different from each other), and

[0031] R 1 Selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues or alkenyl residues, preferably wherein the residues also carry one, two, three, four or more C1 to C4 linear, cyclic or branched alkyl substituents, alkenyl substituents or diene substituents (and wherein the substituents may be identical to or different from each other), and

[0032] R 2 Choose from C6 to C 12 , more preferably C7 to C 12 , most preferably C8 to C 12The straight-chain, cyclic or branched alkyl residue of , preferably further comprises one, two or more functional groups selected from the group consisting of ethers, alcohols and ketones, more preferably further comprises one ether group, or two ether groups, or one alcohol group, or one ketone group, and

[0033] R 3 Selected from hydrogen and C1 to C 10 , preferably a group consisting of a linear or cyclic alkyl residue or alkenyl residue of C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, and most preferably C1 to C5, preferably, wherein the residue also carries one, two, three, four or more linear, cyclic or branched alkyl substituents, alkenyl substituents or diene substituents of C1 to C4 (and wherein the substituents may be the same or different from each other).

[0034] According to another preferred embodiment of the compound of formula (I) of the present invention,

[0035] R is selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues or alkenyl residues, preferably, wherein the residues further carry one, two, three or more substituents selected from the group consisting of methyl and vinyl (and wherein the substituents may be identical to or different from each other), and

[0036] R' is selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues or alkenyl residues, preferably, wherein the residues further carry one, two, three or more substituents selected from the group consisting of methyl and vinyl (and wherein the substituents may be identical to or different from each other), and

[0037] R 1 Selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues or alkenyl residues, preferably, wherein the residues further carry one, two, three or more substituents selected from the group consisting of methyl and vinyl (and wherein the substituents may be identical to or different from each other), and

[0038] R 2 Selected from C6 to C 12 , more preferably C7 to C 12 , most preferably C8 to C 12, a linear, cyclic or branched alkyl residue, preferably further comprising one, two or more functional groups selected from the group consisting of ethers, alcohols and ketones, more preferably further comprising one ether group, or two ether groups, or one alcohol group or a ketone group, and

[0039] R 3 Selected from hydrogen and C1 to C 10 , preferably a linear or cyclic alkyl residue or alkenyl residue of C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, preferably, wherein the residue also carries one, two, three or more substituents selected from the group consisting of methyl and vinyl (and wherein the substituents may be the same or different from each other).

[0040] According to another preferred embodiment of the compound of formula (I) of the present invention,

[0041] R is selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues or alkenyl residues, preferably, wherein the residues further carry one, two, three or more substituents selected from the group consisting of methyl and vinyl (and wherein the substituents may be identical to or different from each other), and

[0042] R' is selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues or alkenyl residues, preferably, wherein the residues further carry one, two, three or more substituents selected from the group consisting of methyl and vinyl (and wherein the substituents may be identical to or different from each other), and

[0043] R 1 Selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues or alkenyl residues, preferably, wherein the residues further carry one, two, three or more substituents selected from the group consisting of methyl and vinyl (and wherein the substituents may be identical to or different from each other), and

[0044] R 2 Choose from C6 to C 12 , more preferably C7 to C 12 , most preferably C8 to C 12The group consisting of a linear, cyclic or branched alkyl residue of , preferably further comprising one, two or more functional groups selected from the group consisting of ethers, alcohols and ketones, more preferably further comprising one ether group, or two ether groups, or one alcohol group, or one ketone group, and

[0045] R 3 For hydrogen.

[0046] The residue R of the compound of formula (I) according to the invention 2 Does not contain any silicon (Si) atoms.

[0047] According to another preferred embodiment of the compound of formula (I) of the present invention, R 2 It is not an n-butyl residue, an n-pentyl residue or an n-hexyl (or 2-propyl) residue.

[0048] According to another preferred embodiment of the compound of formula (I) of the present invention, R 2 is not a residue of the formula (4-hydroxybutyl):

[0049]

[0050] According to an alternative preferred embodiment of the compound of formula (I) of the present invention, R 2 Choose from C4 to C 15 , preferably C4 to C 12 , more preferably C5 to C 12 , more preferably C6 to C 12 , more preferably C7 to C 12 , most preferably C8 to C 12 The group is composed of linear, cyclic or branched alkyl residues and further contains one, two or more ether functional groups.

[0051] According to an alternative preferred embodiment of the compound of formula (I) of the present invention, R 2 Choose from C4 to C 15 , preferably C4 to C 12 , more preferably C5 to C 12 , more preferably C6 to C 12 , more preferably C7 to C 12 , most preferably C8 to C 12 The group is composed of linear, cyclic or branched alkyl residues and also contains an ether functional group.

[0052] According to an alternative preferred embodiment of the compound of formula (I) of the present invention, R 2 Choose from C4 to C 15 , preferably C4 to C 12 , more preferably C5 to C 12 , more preferably C6 to C12 , more preferably C7 to C 12 , most preferably C8 to C 12 The group is composed of a linear, cyclic or branched alkyl residue and also contains two ether functional groups.

[0053] According to an alternative preferred embodiment of the compound of formula (I) of the present invention, R 2 Choose from C4 to C 15 , preferably C4 to C 12 , more preferably C5 to C 12 , more preferably C6 to C 12 , more preferably C7 to C 12 , most preferably C8 to C 12 The group is composed of linear, cyclic or branched alkyl residues and further contains one, two or more alcohol functional groups.

[0054] According to an alternative preferred embodiment of the compound of formula (I) of the present invention, R 2 Choose from C4 to C 15 , preferably C4 to C 12 , more preferably C5 to C 12 , more preferably C6 to C 12 , more preferably C7 to C 12 , most preferably C8 to C 12 The group is composed of straight-chain, cyclic or branched alkyl residues and also contains an alcohol functional group.

[0055] According to an alternative preferred embodiment of the compound of formula (I) of the present invention, R 2 Choose from C4 to C 15 , preferably C4 to C 12 , more preferably C5 to C 12 , more preferably C6 to C 12 , more preferably C7 to C 12 , most preferably C8 to C 12 The group is composed of a linear, cyclic or branched alkyl residue and also contains two alcohol functional groups.

[0056] According to an alternative preferred embodiment of the compound of formula (I) of the present invention, R 2 Choose from C4 to C 15 , preferably C4 to C 12 , more preferably C5 to C 12 , more preferably C6 to C 12 , more preferably C7 to C 12 , most preferably C8 to C 12 The group is composed of linear, cyclic or branched alkyl residues, and also contains one, two or more keto functional groups.

[0057] According to an alternative preferred embodiment of the compound of formula (I) of the present invention, R 2 Choose from C4 to C 15 , preferably C4 to C 12 , more preferably C5 to C 12 , more preferably C6 to C 12 , more preferably C7 to C 12 , most preferably C8 to C 12 The group is composed of a linear, cyclic or branched alkyl residue and also contains a keto functional group.

[0058] According to an alternative preferred embodiment of the compound of formula (I) of the present invention, R 2 Choose from C4 to C 15 , preferably C4 to C 12 , more preferably C5 to C 12 , more preferably C6 to C 12 , more preferably C7 to C 12 , most preferably C8 to C 12 The group is composed of a linear, cyclic or branched alkyl residue and also contains two keto functional groups.

[0059] According to a preferred embodiment of the compound of formula (I) of the present invention, R is selected from the group consisting of:

[0060]

[0061]

[0062] According to another preferred embodiment of the compound of formula (I) of the present invention, R' is selected from the group consisting of:

[0063]

[0064] According to another preferred embodiment of the compound of formula (I) of the present invention, R 1 Selected from the group consisting of:

[0065]

[0066] According to another preferred embodiment of the compound of formula (I) of the present invention, R 2 Selected from the group consisting of:

[0067]

[0068]

[0069]

[0070] According to another preferred embodiment of the compound of formula (I) of the present invention, R 2 Selected from the group consisting of:

[0071]

[0072]

[0073]

[0074] According to another preferred embodiment of the compound of formula (I) of the present invention,

[0075] R is selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues, alkenyl residues or dienyl residues, preferably, wherein the residue also carries one, two, three, four or more C1 to C4 linear, cyclic or branched alkyl substituents, alkenyl substituents or dienyl substituents (and wherein the substituents may be the same or different from each other), and

[0076] R' is selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues, alkenyl residues or dienyl residues, preferably, wherein the residue also carries one, two, three, four or more C1 to C4 linear, cyclic or branched alkyl substituents, alkenyl substituents or dienyl substituents (and wherein the substituents may be the same or different from each other), and

[0077] R 1 Selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues, alkenyl residues or dienyl residues, preferably, wherein the residue also carries one, two, three, four or more C1 to C4 linear, cyclic or branched alkyl substituents, alkenyl substituents or dienyl substituents (and wherein the substituents may be the same or different from each other), and

[0078] R 2 Selected from the group consisting of:

[0079]

[0080]

[0081]

[0082] ,as well as

[0083] R 3 Selected from hydrogen and C1 to C 10 , preferably a group consisting of a C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, and most preferably C1 to C5 straight-chain or cyclic alkyl residue, alkenyl residue or dienyl residue, preferably, wherein the residue also carries one, two, three, four or more C1 to C4 straight-chain, cyclic or branched alkyl substituents, alkenyl substituents or dienyl substituents (and wherein the substituents may be the same or different from each other).

[0084] According to a particularly preferred embodiment of the compound of formula (I) of the present invention,

[0085] R is selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues, alkenyl residues or dienyl residues, preferably, wherein the residue also carries one, two, three, four or more C1 to C4 linear, cyclic or branched alkyl substituents, alkenyl substituents or dienyl substituents (and wherein the substituents may be the same or different from each other), and

[0086] R' is selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues, alkenyl residues or dienyl residues, preferably, wherein the residue also carries one, two, three, four or more C1 to C4 linear, cyclic or branched alkyl substituents, alkenyl substituents or dienyl substituents (and wherein the substituents may be the same or different from each other), and

[0087] R 1 Selected from hydrogen and C1 to C 10 , preferably C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, most preferably C1 to C5, linear or cyclic alkyl residues, alkenyl residues or dienyl residues, preferably, wherein the residue also carries one, two, three, four or more C1 to C4 linear, cyclic or branched alkyl substituents, alkenyl substituents or dienyl substituents (and wherein the substituents may be the same or different from each other), and

[0088] R 2Selected from the group consisting of:

[0089]

[0090]

[0091] ,as well as

[0092] R 3 Selected from hydrogen and C1 to C 10 , preferably a group consisting of a C1 to C9, more preferably C1 to C8, more preferably C1 to C7, more preferably C1 to C6, and most preferably C1 to C5 straight-chain or cyclic alkyl residue, alkenyl residue or dienyl residue, preferably, wherein the residue also carries one, two, three, four or more C1 to C4 straight-chain, cyclic or branched alkyl substituents, alkenyl substituents or dienyl substituents (and wherein the substituents may be the same or different from each other).

[0093] According to another particularly preferred embodiment of the compound of formula (I) of the present invention,

[0094] The residue of the compound of formula (I)

[0095] Selected from the group consisting of:

[0096]

[0097]

[0098]

[0099] and / or, preferably, the residue R of the compound of formula (I) 2 Selected from the group consisting of:

[0100]

[0101]

[0102]

[0103] According to a preferred embodiment, the compounds of formula (I) according to the invention are obtained or obtainable by a [1,4]-addition reaction between an α,β-unsaturated aldehyde or ketone (Michael acceptor, electrophile) and a thiol (Michael donor, nucleophile),

[0104] - The α,β-unsaturated aldehyde or ketone is selected from the group consisting of (the compound groups shown in the "Structure" column of Table 1 below):

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111] Table 1

[0112] - The thiol is selected from the group consisting of (the compound groups shown in the "Structure" column of Table 2 below):

[0113]

[0114]

[0115]

[0116]

[0117]

[0118] Table 2

[0119] According to a preferred embodiment, citral, ie a mixture of neral and geranal as shown in Table 1 above, is used as the α,β-unsaturated aldehyde (mixture) for forming the compound of formula (I).

[0120] The compounds of formula (I) according to the present invention

[0121]

[0122] A (pleasant smelling, high impact) thiol and a (pleasant smelling, high impact) α,β-unsaturated aldehyde or ketone, preferably selected from the group consisting of the compounds shown in the "Structure" column of Table 2 above, and a (pleasant smelling, high impact) α,β-unsaturated aldehyde or ketone, preferably selected from the group consisting of the compounds shown in the "Structure" column of Table 1 above, are released by the following decomposition reaction:

[0123]

[0124] Preferably, the release is triggered by a specific pH value and / or temperature, UV light, water and / or oxygen.

[0125] According to a particularly preferred embodiment, the compound of formula (I) according to the present invention is selected from the group consisting of the following (the group of compounds shown in the "Structure" column of Table 3 below):

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138] Table 3

[0139] According to a particularly preferred embodiment, the compounds of formula (I) according to the invention are not

[0140]

[0141] Another aspect of the present invention relates to a fragrance substance mixture, preferably an essential oil, which comprises or consists of the following components:

[0142] (i) one or more compounds of formula (I) as defined herein;

[0143] as well as

[0144] (ii) one or more other aromatic substances.

[0145] The one or more further aroma substances are different from the compounds of formula (I) according to the invention.

[0146] Examples of other aromatic substances that can be advantageously combined with the compounds of formula (I) as defined herein within the scope of the present invention are known to the person skilled in the art and can be found in: S. Arctander, "Perfume and Flavor Materials", Volumes I and II, Montclair, New Jersey, 1969, self-published; or K. Bauer et al., "Common Fragrance and Flavors Materials", 4th edition, Wiley VCH, Weinheim 2001.

[0147] According to a preferred embodiment of the aromatic substance mixture of the present invention, preferably an essential oil, the total amount of the compounds of formula (I) as defined herein in the aromatic substance mixture is 0.1 wt% to 3 wt%, preferably 0.5 wt% to 2.5 wt%, particularly preferably 1 wt% to 2 wt%, based on the total mass of the aromatic substance mixture.

[0148] Another aspect of the invention relates to a method for producing a mixture of aromatic substances as defined above, preferably essential oils, comprising or consisting of the following steps:

[0149] One or more compounds of formula (I) as defined herein are mixed with one or more other fragrance substances.

[0150] Furthermore, the aromatic substance mixture according to the invention, preferably an essential oil, can be adsorbed on a carrier which provides both a fine distribution of the aromatic substance mixture, preferably an essential oil, in the fragrance product and a controlled release during application. Such a carrier can be: a porous inorganic material, such as light sulfate, silica gel, zeolite, gypsum, clay, clay particles, aerated concrete, etc.; or an organic material, such as wood, cellulose-based materials, sugar, dextrin (such as maltodextrin); or a plastic, such as polyvinyl chloride (PVC), polyvinyl acetate or polyurethane. The combination of the aromatic substance mixture according to the invention, preferably an essential oil, and a carrier should also be understood as the aromatic substance mixture according to the invention, preferably an essential oil, or can be presented as a fragrance product according to the invention (as described below).

[0151] The aroma mixture of the invention, preferably an essential oil, or an aroma product (as described below) can also be microencapsulated, spray-dried, or can be provided as an inclusion compound or as an extruded product, and the aroma mixture, preferably an essential oil, can be added in this form, for example, to an aroma product to be aromatized (as described below).

[0152] If desired, the properties of this modified mixture or product can be further optimized by so-called "coating" with suitable materials, preferably waxy plastics such as polyvinyl alcohol, with a view to a more targeted release of aroma. The resulting product also represents the product of the invention.

[0153] For example, microencapsulation can be achieved by the so-called coacervation process using capsule materials such as polyurethanes or soft gelatin.

[0154] The spray-dried products are preferably produced by spray-drying emulsions or dispersions containing the aroma substance mixture according to the invention, preferably essential oils, whereby modified starches, proteins, dextrins and vegetable gums can be used as carriers.

[0155] The inclusion complex can be prepared, for example, by dissolving a dispersion of the fragrance substance mixture according to the invention, preferably an essential oil, together with a cyclodextrin or a urea derivative in a suitable solvent, for example water.

[0156] Extruded products can be obtained, for example, by using the aromatic substance mixture according to the invention, preferably an essential oil, together with a suitable waxy substance, by extrusion and then, if desired, solidifying in a suitable solvent, for example isopropanol.

[0157] Another aspect of the present invention relates to a fragrance product comprising one or more compounds of formula (I) as defined herein or a mixture of fragrance substances as defined herein, preferably an essential oil, preferably in a sensory effective amount.

[0158] Advantageously, one or more compounds of formula (I) according to the invention positively impart or modify the odor of a fragrance product to which the compound of formula (I) according to the invention is added.

[0159] According to a preferred embodiment, the fragrance product is selected from the group consisting of: fragrance extracts; perfumes; eau de toilette; aftershave; cologne; pre-shave products; cologne sprays; scented cleansing cloths; acidic, alkaline and neutral detergents; textile fresheners; ironing aids; washing liquids; washing powders; clothing pretreaters; fabric softeners; washing soaps; washing tablets; disinfectants; surface disinfectants; air fresheners; aerosol sprays; waxes and polishes; personal care products; hand creams and lotions; foot creams and lotions; depilatory creams and lotions; aftershave creams and lotions; tanning creams and lotions; hair care products; deodorants and antiperspirants; decorative cosmetics; candles; lamp oils; incense sticks; insecticides; insect repellents; and fuels, most preferably fabric softeners.

[0160] According to a preferred embodiment of the fragrance product of the present invention, based on the total mass of the fragrance product, the proportion of the total amount of the aromatic substance mixture, preferably essential oil, as defined herein in the fragrance product is 0.1wt% to 3wt%, preferably 0.5wt% to 2.5wt%, and particularly preferably 1wt% to 2wt%.

[0161] Another aspect of the present invention relates to a method for producing a fragrance product, preferably a fragrance product as defined herein, comprising or consisting of the following steps:

[0162] (i) providing one or more compounds of formula (I) as defined herein or a fragrance mixture as defined herein, preferably an essential oil;

[0163] (ii) providing one or more other components of the flavor product to be produced;

[0164] as well as

[0165] (iii) contacting or mixing the other components provided in step (ii) with an organoleptically effective amount of the components provided in step (i).

[0166] Another aspect of the present invention relates to the use of a compound of formula (I) as defined herein as a precursor for the (controlled) release of one, two, three or more different pleasant smelling fragrance substances, preferably wherein the two or more different fragrance substances are released and / or sensory perceived (if two or more different fragrance substances are released) at the same or different points in time, preferably at different points in time.

[0167] Another aspect of the present invention relates to the use of a compound of formula (I) as defined herein as a precursor for the (controlled) release of a pleasant-smelling thiol and a pleasant-smelling α,β-unsaturated aldehyde or ketone, preferably wherein the thiol and the α,β-unsaturated aldehyde or ketone are released and / or sensory perceived at the same or different time points, preferably at different time points.

[0168] Another aspect of the invention relates to the use of a compound of formula (I) as defined herein as a precursor for the (controlled) release of a (pleasant smelling) thiol, and / or, preferably, and a (pleasant smelling) α,β-unsaturated aldehyde or ketone, the thiol being selected from the group consisting of:

[0169]

[0170]

[0171]

[0172] The α,β-unsaturated aldehyde or ketone is selected from the group consisting of:

[0173]

[0174]

[0175]

[0176] Preferably, the thiol and the α,β-unsaturated aldehyde or ketone are released and / or sensory perceived at the same or different time points, preferably at different time points.

[0177] Another aspect of the invention relates to the use of a compound of formula (I) as a precursor for the (controlled) release of a (pleasant smelling) thiol, and / or, preferably and a (pleasant smelling) α,β-unsaturated aldehyde or ketone selected from the group consisting of

[0178] The residue of the compound is selected from the group consisting of:

[0179]

[0180]

[0181]

[0182] and / or, preferably, wherein the residue R 2 Selected from the group consisting of:

[0183]

[0184]

[0185]

[0186] The thiol is selected from the group consisting of:

[0187]

[0188]

[0189]

[0190] The α,β-unsaturated aldehyde or ketone is selected from the group consisting of:

[0191]

[0192]

[0193]

[0194] Preferably, the thiol and the α,β-unsaturated aldehyde or ketone are released and / or sensory perceived at the same or different time points, preferably at different time points.

[0195] The thiols and α,β-unsaturated aldehydes or ketones released from the compounds of formula (I) according to the invention and / or the thiols and α,β-unsaturated aldehydes or ketones used to form the compounds of formula (I) according to the invention may be in the form of pure diastereomers or stereoisomers, or in the form of any mixture of said isomers.

[0196] According to a preferred embodiment of the use according to the invention, the thiol released from the compound of formula (I) as defined herein is released and / or organoleptically perceived before the release of the α,β-unsaturated aldehyde or ketone from the (same) compound of formula (I) as defined herein.

[0197] According to an alternative embodiment of the use according to the invention, the α,β-unsaturated aldehyde or ketone released from the compound of formula (I) as defined herein is released and / or sensory perceived before the release of the thiol from the (same) compound of formula (I) as defined herein.

[0198] According to a further alternative embodiment of the use according to the invention, the thiol released from the compound of formula (I) as defined herein and the α,β-unsaturated aldehyde or ketone released from the (same) compound of formula (I) as defined herein are released and / or sensory perceived simultaneously.

[0199] Preferably, the pleasant smelling thiol has one or more odor notes selected from the group consisting of: grapefruit, black currant, onion, fruity, exotic fruit, guava, smoker's breath, sulfur, (burnt) plastic, (mint) green, rose oxide, green pepper, liver sausage, buchu (leek), gasoline, juicy, natural, cat grass, broth ("Fleischbrühe"), custard, camembert, cheese from the fridge, fresh, hot rubber, petroleum, violet, black currant, catnip (grass), orange peel, fennel, mushroom, soup, leek, citrus fruit, peach, meat, pine, mango, durian, jackfruit, artichoke and apricot;

[0200] More preferably, the pleasant smelling thiol has one or more odor notes selected from the group consisting of grapefruit, black currant, onion, fruity, exotic fruit, guava, sulfur, (mint) green, rose oxide, green pepper, liver sausage, buchu (leek), juicy, natural, cat grass, broth ("Fleischbrühe"), custard, Camembert cheese, fresh, violet, black currant, catnip (grass), orange peel, fennel, mushroom, soup, leek, citrus fruit, peach, meat, pine, mango, durian, jackfruit, artichoke and apricot.

[0201] Another aspect of the invention relates to a method for the (controlled) release of one, two, three or more different pleasant smelling fragrance substances, the method comprising or consisting of the following steps:

[0202] (a) providing a compound of formula (I) as defined herein or a fragrance mixture as defined herein (comprising one or more compounds of formula (I) as defined herein) or a fragrance product as defined herein (comprising one or more compounds of formula (I) as defined herein);

[0203] (b) optionally, applying or introducing the compound of formula (I) or the aromatic substance mixture or the fragrance product in step (a), preferably in an organoleptically effective amount, to the hair or skin or textile fibers or the surface to be perfumed, or to the ambient air to be perfumed; and

[0204] (c) releasing one, two, three or more different pleasant smelling aroma substances from the compound of formula (I), preferably, wherein two or more different pleasant smelling aroma substances are released and / or sensory perceived at the same or different time points, preferably at different time points (if two or more different aroma substances are released).

[0205] Another aspect of the present invention relates to a method for the (controlled) release of pleasant smelling thiols and pleasant smelling α,β-unsaturated aldehydes or ketones, the method comprising or consisting of the following steps:

[0206] (a) providing a compound of formula (I) as defined herein or a fragrance mixture as defined herein (comprising one or more compounds of formula (I) as defined herein) or a fragrance product as defined herein (comprising one or more compounds of formula (I) as defined herein);

[0207] (b) optionally, applying or introducing the compound of formula (I) or the aromatic substance mixture or the fragrance product in step (a), preferably in an organoleptically effective amount, to the hair or skin or textile fibers or the surface to be perfumed, or applying or introducing it into the ambient air to be perfumed;

[0208] (c) releasing a pleasant smelling thiol and a pleasant smelling α,β-unsaturated aldehyde or ketone from the compound of formula (I), preferably, wherein the pleasant smelling thiol and the pleasant smelling α,β-unsaturated aldehyde or ketone are released and / or sensory perceived at the same or different time points, preferably at different time points.

[0209] According to a preferred embodiment of the process according to the invention, the thiol released in step (c) from the compound of formula (I) as defined herein is released and / or sensory perceived before the release of the α,β-unsaturated aldehyde or ketone from the (same) compound of formula (I) as defined herein in step (c).

[0210] According to another embodiment of the method of the present invention, the α,β-unsaturated aldehyde or ketone released in step (c) from the compound of formula (I) as defined herein is released and / or sensory perceived before the release of the thiol from the (same) compound of formula (I) as defined herein in step (c).

[0211] According to a further embodiment of the method of the present invention, the thiol released in step (c) from the compound of formula (I) as defined herein and the α,β-unsaturated aldehyde or ketone released in step (c) from the (same) compound of formula (I) as defined herein are released and / or sensory perceived simultaneously.

[0212] Another aspect of the invention relates to a method for the (controlled) release of a (pleasant smelling) thiol, and / or, preferably, and a (pleasant smelling) α,β-unsaturated aldehyde or ketone, the thiol being selected from the group consisting of:

[0213]

[0214]

[0215]

[0216] The α,β-unsaturated aldehyde or ketone is selected from the group consisting of:

[0217]

[0218]

[0219]

[0220] The method comprises or consists of the following steps:

[0221] (a) providing a compound of formula (I) (or a fragrance mixture or fragrance product comprising a compound of formula (I) as defined above), wherein the residue of the compound of formula (I)

[0222]

[0223] Selected from the group consisting of:

[0224]

[0225]

[0226]

[0227] and / or, preferably, wherein the residue R 2 Selected from the group consisting of:

[0228]

[0229]

[0230] (b) optionally, applying or introducing the compound of formula (I) of step (a) (or a fragrance mixture or fragrance product comprising the compound of formula (I) of step (a)) to the hair or skin or textile fibers or the surface to be perfumed, or applying or introducing into the ambient air to be perfumed, preferably in an organoleptically effective amount;

[0231] (c) releasing the (pleasant odor) thiol and / or the (pleasant odor) α,β-unsaturated aldehyde or ketone from the compound of formula (I), preferably, wherein the (pleasant odor) thiol and the (pleasant odor) α,β-unsaturated aldehyde or ketone are released and / or sensory perceived at the same or different time points, preferably at different time points.

[0232] Another aspect of the present invention relates to a thiol selected from the group consisting of:

[0233]

[0234]

[0235] During the research on the basis of the present invention it was surprisingly found that thiols as defined above, preferably after release from the compounds of formula (I) according to the invention, can be used as pleasant-smelling high-impact fragrances.

[0236] The thiol according to the present invention can be obtained by applying the method disclosed in WO 2019 / 037862 A1.

[0237] A description of the odor of the thiols according to the invention can be found in Table 2 above.

[0238] Therefore, a further aspect of the present invention relates to the use of one or more thiols according to the invention as fragrance substances.

[0239] Another aspect of the present invention relates to a method for aromatizing hair, skin, textile fibers, surfaces and / or ambient air, the method comprising or consisting of the following steps:

[0240] (a) Provide

[0241] (i) one or more thiols as defined herein, preferably also a surfactant or a mixture of surfactants, or

[0242] (ii) one or more compounds of formula (I) as defined herein, preferably also providing a surfactant or a mixture of surfactants, or

[0243] (iii) a fragrance mixture as defined herein, preferably a fragrance mixture containing a surfactant or a mixture of surfactants, or

[0244] (iv) a fragrance product as defined herein, preferably the fragrance product comprises a surfactant or a mixture of surfactants;

[0245] as well as

[0246] (b) applying or introducing (i) the thiol and preferably also a surfactant or a surfactant mixture, or (ii) the compound and preferably also a surfactant or a surfactant mixture, or (ii) the fragrance mixture, or (iii) the fragrance product of step (a) in an organoleptically effective amount to the hair or skin or textile fibers or surfaces to be perfumed, or to the ambient air to be perfumed.

[0247] Another aspect of the invention relates to the use of a compound of formula (I) as defined herein or a fragrance substance mixture as defined herein, preferably an essential oil, as aromatizing ingredient.

[0248] Another aspect of the invention relates to the use of a compound of formula (I) as defined herein or a fragrance substance mixture as defined herein, preferably an essential oil, for perfuming hair, skin, textile fibres, surfaces and / or ambient air.

[0249] Another aspect of the invention relates to a fragrance substance mixture as defined herein, preferably an essential oil, wherein the amount of the compound of formula (I) is

[0250] (a) sufficient to mask or reduce the unpleasant odor impression of one or more aromatic substances in a mixture of aromatic substances,

[0251] and / or

[0252] (b) sufficient to enhance the pleasant odor impression of one or more other aromatic substances in a mixture of aromatic substances.

[0253] Another aspect of the invention relates to the use of one or more compounds of formula (I) as defined herein or a fragrance mixture as defined herein, preferably an essential oil, for:

[0254] (a) used to mask or reduce the unpleasant odour impression of one or more unpleasant odour substances;

[0255] and / or

[0256] (b) for enhancing the pleasant odor impression of one or more pleasant odor substances.

[0257] Another aspect of the present invention relates to a method for:

[0258] (a) masking or reducing the unpleasant odour impression of one or more unpleasant odour substances;

[0259] and / or

[0260] (b) enhancing the pleasant odor impression of one or more pleasant odorous substances,

[0261] The method comprises the following steps:

[0262] Unpleasant odor substances and / or pleasant odor substances are mixed with one or more compounds of formula (I) as defined herein or with a fragrance substance mixture as defined herein, preferably an essential oil, wherein the amount of one or more compounds of formula (I) as defined herein or the fragrance substance mixture as defined herein, preferably an essential oil, is sufficient to (a) reduce or mask the unpleasant odor impression of the unpleasant odor substances and / or (b) enhance the pleasant odor impression of the pleasant odor substances.

[0263] What is stated herein with respect to the aroma substance mixtures, fragrance products, methods, uses and thiols according to the invention also applies to the preferred embodiments of the compounds of formula (I) according to the invention and vice versa.

[0264] Hereinafter, the present invention will be explained in more detail by way of examples. DETAILED DESCRIPTION

[0265] Example:

[0266] Synthesis method of precursor according to the present invention

[0267] 1. Synthesis of the precursor 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyl-1-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-1-one (compound of formula (I) according to the present invention)

[0268]

[0269] In a 500 ml stirring apparatus equipped with a magnetic stirrer, reflux condenser, thermometer, dropping funnel and ice bath, 5.8 g of 1,1,3,3-tetramethylguanidine, 9.4 g of 2-methyl-1-(4-methyltetrahydropyran-2-yl)propanethiol and 200 ml of tetrahydrofuran were added under a nitrogen atmosphere at 0°C. 8.1 g of δ-damascone were added dropwise at 0-5°C over 1 hour. Stirring was continued at 0-5°C for 6 hours for the subsequent reaction. The mixture was washed twice with a saturated sodium bicarbonate solution at room temperature, and then the solvent was evaporated on a rotary evaporator. 16.8 g of crude product 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyl-1-(2,6,6-trimethyl-cyclohex-3-en-1-yl)butane-1-one was obtained with a GC content of 90%. For further purification, the crude product was chromatographed on a silica gel column using hexane: diethyl ether (10: 1) as the eluent to give 4.0 g of 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyl-1-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-1-one with a GC content of 94%.

[0270] Mass spectrometry analysis of products:

[0271] m / z: 99(100), 123(35), 81(35), 43(33), 69(27), 115(24), 55(18), 225(17), 41(17), 192(16).

[0272] 2. Synthesis of the precursor 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]-sulfanyl decanal (compound of formula (I) according to the present invention)

[0273]

[0274] In a 500 ml stirring apparatus equipped with a magnetic stirrer, reflux condenser, thermometer, dropping funnel and ice bath at 0°C under a nitrogen atmosphere, 5.8 g of 1,1,3,3-tetramethylguanidine, 9.4 g of 2-methyl-1-(4-methyltetrahydropyran-2-yl)propanethiol and 200 ml of tetrahydrofuran were placed. At 0-5°C, 6.4 g of 2-(E)-decenal were added dropwise over 1 hour. For the subsequent reaction, stirring was continued at 0-5°C for 6 hours. The mixture was washed twice with saturated sodium bicarbonate solution at room temperature, and then the solvent was evaporated on a rotary evaporator. 14.6 g of crude product 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyldecanal was obtained with a GC content of 76%. For further purification, the crude product was chromatographed on a silica gel column using hexane: diethyl ether (10:1) as eluent. 4.2 g of 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyldecanal were obtained with a GC content of 90%.

[0275] Mass spectrometry analysis of products:

[0276] m / z: 99(100), 43(23), 55(17), 81(13), 41(13), 69(11), 57(10), 98(8), 29(7), 100(7).

[0277] 3. Synthesis of the precursor 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanylhexanal (compound of formula (I) according to the present invention)

[0278]

[0279] In a 500 mL stirring apparatus equipped with a magnetic stirrer, reflux condenser, thermometer, dropping funnel and ice bath, 12.4 g of 1,1,3,3-tetramethylguanidine, 20.4 g of 2-methyl-1-(4-methyltetrahydropyran-2-yl)propane-1-thiol and tetrahydrofuran (400 mL) were added at 0° C. under nitrogen atmosphere. 12.7 g of (E)-hex-2-enal were added dropwise at 0-5° C. over 1 hour. For the subsequent reaction, stirring was continued at 0-5° C. for 6 hours. The mixture was washed twice with saturated sodium bicarbonate solution at room temperature, and then the solvent was evaporated on a rotary evaporator. 30.9 g of crude product 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanylhexanal were obtained. For further purification, the crude product was chromatographed on a silica gel column using hexane: diethyl ether (10:1) as eluent. 26.8 g of 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanylhexanal were obtained with a GC content of 90%.

[0280] Mass spectrometry analysis of products:

[0281] m / z: 99(100), 43(24), 55(15), 41(13), 81(12), 69(12), 100(6), 57(6), 170(6), 29(5), 98(5).

[0282] 4. Synthesis of the precursor 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyl-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-butan-2-one (compound of formula (I) according to the present invention)

[0283]

[0284] In a 50 mL stirring apparatus equipped with a magnetic stirrer, a reflux condenser, a thermometer, a dropping funnel and an ice bath, 0.02 g of 1,1,3,3-tetramethylguanidine, 14.1 g of 2-methyl-1-(4-methyltetrahydropyran-2-yl)propane-1-thiol and tetrahydrofuran (40 mL) were added at 0° C. under a nitrogen atmosphere. 14.4 g of (E)-[4]-(2,6,6-trimethylcyclohex-1-en-1-yl)but-3-en-2-one was added dropwise over 1 hour at 0-5° C. For the subsequent reaction, stirring was continued at 0-5° C. for 6 hours. The mixture was washed twice with a saturated sodium bicarbonate solution at room temperature, and the solvent was evaporated on a rotary evaporator. 28.5 g of crude product 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyl-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-butan-2-one were obtained. For further purification, the crude product was chromatographed on a silica gel column using hexane:diethyl ether (10:1) as eluent. 18.9 g of 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyl-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-butan-2-one were obtained with a GC content of 90%.

[0285] Mass spectrometry analysis of products:

[0286] m / z: 43(100), 99(78), 177(35), 175(33), 133(29), 41(29), 135(27), 55(24), 81(19), 69(18), 193(15), 149(15), 192(12), 93(12), 29(11), 91(11), 79(10).

[0287] 5. Synthesis of the precursor 8-ethoxytricyclo[5.2.1.02,6]decane-4-sulfanyl-1-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-1-one (compound of formula (I) according to the present invention)

[0288]

[0289] In a 50 mL stirring apparatus equipped with a magnetic stirrer, reflux condenser, thermometer, dropping funnel and ice bath, 0.02 g of 1,1,3,3-tetramethylguanidine, 16.4 g of 8-ethoxytricyclo[5.2.1.02,6]decane-4-thiol and tetrahydrofuran (40 mL) were added at 0°C under nitrogen atmosphere. 14.4 g of (E)-[1]-(2,6,6-trimethylcyclohex-3-en-1-yl)but-2-en-1-one was added dropwise over 1 hour at 0-5°C. Stirring was continued at 0-5°C for 6 hours for the subsequent reaction. The mixture was washed twice with saturated sodium bicarbonate solution at room temperature, and the solvent was evaporated on a rotary evaporator. 30.4 g of crude product 8-ethoxytricyclo[5.2.1.02,6]decane-4-sulfanyl-1-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-1-one were obtained.

[0290] Mass spectrometry analysis of products:

[0291] m / z: 133(100), 67(58), 123(51), 91(48), 81(45), 239(41), 79(41), 107(41), 41(37), 69(37), 29(35), 105(24), 103(21), 55(20), 43(18), 122(17), 77(17).

[0292] The synthesis method of thiol according to the present invention

[0293] 1.2-Methyl-1-[4-methyltetrahydropyran-2-yl]propane-1-thiol

[0294] Preparation of 2-methyl-1-[4-methyltetrahydropyran-2-yl]propane-1-thiol according to WO 2019 / 037862 A1:

[0295]

[0296] 2.46 g of 2,2-azobis-(2-methylpropionitrile, AIBN) was added to 463 g of 4-methyl-2-(2-methyl-prop-1-enyl)tetrahydropyran and 228 g of thioacetic acid at 5-10° C. and stirred at room temperature for 30 minutes. The mixture was then slowly heated to 60° C. and stirred at 60° C. for 10 hours until complete conversion. After cooling to room temperature, the product was obtained by distillation (2.0 mbar, 104-110° C.), yielding 527.69 g (76%) of 2-methyl-(1-4-methyltetrahydropyran-2-yl)propyl-thioacetate as an isomer mixture.

[0297] Electron impact mass spectrometry (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).

[0298]

[0299] A solution of 501 g of 2-methyl-(1-4-methyltetrahydropyran-2-yl)propyl-thioacetate in anhydrous methanol (3.3 L) was treated with 300 g of potassium carbonate under nitrogen and stirred overnight until complete conversion. The mixture was then acidified with 2M hydrochloric acid (1 L) and 1 I of H2O and 1.5 L of Et2O were added. The organic phase was separated and the aqueous phase was extracted with 500 mL of Et2O. The combined organic phases were washed with brine (500 mL), dried over sodium sulfate and reduced in vacuo. The crude product was purified by distillation (3.6 mbar, 99-102° C.) to give 372 g (91%) of 2-methyl-1-[4-methyltetrahydropyran-2-yl]propane-1-thiol as an isomeric mixture.

[0300] EI-MS m / z(%):188(1,[M] + ), 170(1), 139(1), 111(1), 99(100), 81(19), 69(12), 55(19), 43(22), 29(5).

[0301] 2.8-Ethyloxytricyclo[5.2.1.02,6]decane-4-thiol

[0302]

[0303] 2.91 g of 2,2-azobis-(2-methylpropionitrile, AIBN) was added to 583 g of 8-methoxytricyclo[5.2.1.02,6]dec-3-ene and 279 g of thioacetic acid at 5-10° C. and stirred at room temperature for 30 minutes. The mixture was then slowly heated to 60° C. and stirred at 60° C. for 10 hours until complete conversion. After cooling to room temperature, the product was obtained by distillation (2.0 mbar, 104-110° C.), yielding 773 g (91%) of (8-methoxytricyclo-4-[5.2.1.02,6]decyl)thioacetate as an isomer mixture.

[0304]

[0305] A solution of 538 g of (8-methoxytricyclo-4-[5.2.1.02,6]decyl)thioacetate in anhydrous methanol (3.3 L) was treated with 300 g of potassium carbonate under nitrogen and stirred overnight until complete conversion. The solvent was evaporated under reduced pressure and 400 mL of methyl tert-butyl ether (MTBE) was added. The organic phase was separated and the aqueous phase was extracted with 200 mL of MTBE. The combined organic phases were washed with saturated sodium bicarbonate solution, sodium sulfite solution and brine, dried over sodium sulfate and reduced under reduced pressure. The crude product was purified by distillation (3.6 mbar, 99-102° C.) to give 376 g (90%) of 8-ethoxytricyclo[5.2.1.02,6]decane-4-thiol as an isomer mixture.

[0306] Mass spectrometry analysis of products:

[0307] m / z: 166(100), 91(75), 92(75), 133(72), 79(57), 132(48), 105(47), 117(45), 93(44), 67(37), 106(35), 212(28), 77(26), 29(25), 41(25), 66(24), 137(24).

[0308] The product according to the invention

[0309] 1. Fabric Softener

[0310]

[0311] Table 4: Fabric softener formulation according to the present invention

[0312] 2. Deodorant

[0313]

[0314]

[0315] Table 5: Deodorant formulation according to the present invention

[0316] 3. Shampoo

[0317]

[0318] Table 6: Shampoo formulation according to the invention

[0319] Sensory analysis

[0320] 1. Headspace Gas Chromatography / Mass Spectrometry

[0321] Application of precursors in fabric softeners (hand wash):

[0322] 1.0 g of a solution containing 1.0% of the compound of formula (I) according to the present invention in a fabric softener (see fabric softener composition in Table 7 below) was added to a 2 liter beaker containing 1 liter of H2O and mixed briefly to form a homogeneous solution.

[0323]

[0324] Table 7: Composition of fabric softeners used

[0325] Five cotton fabrics (16x17 cm each, 25 g) were added and stirred at room temperature for 30 minutes using a magnetic stirrer. Each piece of cotton fabric was then individually wrung (about 60 g each) and dried on a drying rack in a homemade closed drying chamber (1431) with constant air circulation and a temperature of 25°C. At specified time points, volatiles were sampled at a continuous flow rate of 500 ml / min via a Gerstel gas sampling system. Adsorb on the adsorption tube for 2 minutes.

[0326] After drying in a drying room for 1 h, two pieces of fabric were used for additional measurements in a homemade glass tube. Two pieces of fabric were taken from the drying rack and placed in a glass tube (0.441) at room temperature. The volatiles were adsorbed using a Gerstel gas sampling system at a continuous gas flow rate (500 ml / min), first in the waste The adsorption was carried out on the adsorption tube for 58 minutes and then on a new Adsorb on the adsorption tube for 2 minutes. Then continue to Samples were taken from the adsorption tube until the specified time point, after 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 24 hours, 48 ​​hours, 72 hours, in a new The samples were taken from the adsorption tubes for 2 minutes each time. These adsorption tubes were then desorbed at 260°C on a Gerstel thermal desorber. The volatiles were injected into an Agilent 6890 gas chromatograph equipped with a DB-1MS column (30m, 0.25mm, 0.25μm) and connected to an Agilent mass spectrometer 5973N. The volatiles were eluted using a helium (He) gas flow at a flow rate of 1.4ml / min, and the temperature gradient started from 50°C (lasting 4 minutes) and increased to 260°C at a rate of 8°C / min.

[0327] The headspace concentration was calculated in EtOH using the corresponding aromatic materials (0.1 ng / l, 0.25 ng / l, 0.5 ng / l, 1.0 ng / l, 2.5 ng / l, 5.0 ng / l) with different concentrations by external standard calibration. The corresponding aromatic materials are aromatic materials released from the specific precursor / compound of formula (I), i.e., the corresponding α, β-unsaturated carbonyl compounds and thiol compounds. Each calibration solution (1 μl) was injected into a clean empty adsorption tube and desorbed and analyzed using the same conditions as described above.

[0328] Figure 1 : Aroma release profile of the precursor 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyldecanal (obtained according to Method 2 in the Precursor Synthesis Method described above) measured by Method 1 in the sensory analysis described above.

[0329] Figure 2 : Aroma release profile of the precursor 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyl-1-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-1-one (obtained according to Method 1 in the precursor synthesis method described above) measured by Method 1 in the sensory analysis described above.

[0330] Figure 1 and Figure 2The release of 2-methyl-1-(4-methyltetrahydropyran-2-yl)propanethiol and the corresponding α, β-unsaturated carbonyl compounds is shown, which are released from the compounds of formula (I) obtained according to methods 1 and 2 in the precursor synthesis method described above. The x-axis in the figure represents the time period for measurement. On the y-axis, the headspace concentrations of the two components released from the compounds of formula (I) are shown respectively (determined according to method 1 in the sensory analysis described above). As can be seen from the figure, on freshly washed / wet clothes, the thiol compounds are strongly released and can be sensed. On the other hand, on dry clothes, the obvious release of α, β-unsaturated carbonyl compounds is delayed for a period of time and occurs after a few hours (2-decenal: 2-48 hours, δ-damasconone: 24-72 hours). These analytical results prove that while the (controlled) decomposition of the compounds of formula (I) according to the present invention is carried out, α, β-unsaturated aldehydes or ketones are released over time, and are consistent with the sensory evaluation of the washing test (see below). By controlled decomposition of the compound of formula (I), the α,β-unsaturated aldehyde or ketone is advantageously perceived on dry laundry for a long time. In addition, the high impact thiol compound improves the overall odor of freshly washed laundry without generating undesirable or unpleasant odors.

[0331] For comparison purposes, the experiment was repeated, but instead of the compound of formula (I) according to the invention, 1.0 g of a mixture of an α,β-unsaturated carbonyl compound (hexenal) and a mercaptan (2-methyl-1-(4-methyltetrahydropyran-2-yl)propane-1-thiol) was used.

[0332]

[0333]

[0334] Table 8: Aroma release of the precursor 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanylhexanal, a compound of formula (I) according to the invention, and a mixture of 34% of hexanal and 66% of 2-methyl-1-(4-methyltetrahydropyran-2-yl)propane-1-thiol.

[0335] It can be seen that the aroma released from the compound of formula (I) according to the present invention is significantly different from the aroma released from the mixture of α,β-unsaturated carbonyl compounds and thiols, because the released aromatic material is produced by the partial degradation of the compound of formula (I) according to the present invention over time. Unexpectedly, it was observed that the peak of thiol release was between 0-1 hours, while the release of hexenal reached a peak at 4-7 hours, which surprisingly showed that the compound of formula (I) according to the present invention can provide two aromatic materials with pleasant smells at different time points.

[0336] 2. Washing test

[0337] As described below, the compounds of formula (I) according to the present invention (obtained according to methods 1 and 2 in the precursor synthesis method described above) were subjected to sensory evaluation after washing application, and the test results shown in the following Table 9 were given.

[0338] - In practical use tests, the corresponding compounds of formula (I) according to the present invention are applied in essential oils

[0339] -Essential oil dosage: 1 wt% in fabric softener (the composition of fabric softener is shown in Table 7 above)

[0340] - Precursor dosage in essential oil: 2wt%

[0341] - Wash cotton fabrics in a washing machine at 30°C on a short cycle

[0342] - The sensory evaluation was conducted by a panel of 5 people. The intensity given in Table 9, ranging from 0 (no odor) to 9 (very strong odor), is the average of three evaluations by three panelists, respectively. The odor description given in Table 9 is the average of five evaluations by five panelists, respectively.

[0343]

[0344] Table 9

[0345] 3. Fabric softener

[0346] Aromatic fabric softener samples were prepared by mixing appropriate amounts of the compound of formula (I) and dipropylene glycol (DPG) into essential oils and adding 1% of the resulting fragrance mixture to unaromatized fabric softener.

[0347] 2 kg of cotton towels were washed in a European washing machine (Express 20 program, 20°C, 800 rpm) using 30 g of an aromatic fabric softener (composition of the fabric softener is shown in Table 7). The fabrics were dried overnight on a clothesline and placed on a table for evaluation after 24, 48 and 72 hours. The fabrics were evaluated by 12 trained panelists. The fragrance intensity was evaluated on a scale from no odor (0) to the strongest odor imaginable (10). The panelists were also asked to select which sample had a higher perceived intensity.

[0348] It was concluded that the aroma perception was significantly stronger with the compound of formula (I) compared to an equal amount of δ-damascone. To emphasize this point, a cotton towel was subjected to headspace GC / MS analysis according to method 1 in the sensory analysis described above, and it was found that the cotton towel washed with the essential oil including the compound of formula (I) had significantly higher headspace concentrations of δ-damascone.

[0349]

[0350] Table 10: Average strength

[0351]

[0352] Table 11: Probability of the most intense samples

[0353]

[0354]

[0355] Table 12: Composition of essential oils used

[0356] Aroma release of a mixture of the compound 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]-sulfanyl-1-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-1-one of formula (I) and 50% of delta-damascone and 50% of DPG:

[0357]

[0358] Table 13

[0359] 4. Deodorant

[0360] Using synthetic skin (Vitro The artificial skin model was prepared by using fat, cellulose and agar.

[0361] Aromatized deodorant samples were prepared by mixing appropriate amounts of the compound of formula (I) and DPG into essential oils and adding 1% of the resulting fragrance mixture to an unaromatized deodorant base.

[0362] 100 mg of the aromatized deodorant was applied to the artificial skin and spread evenly for 15 seconds. The model was then placed on a hot plate (43°C) and evaluated by 6 trained panelists after 0, 4, 24 and 48 hours. The fragrance intensity was rated on a scale from no odor (0) to the strongest odor imaginable (9).

[0363] It was concluded that the intensity of the aroma was significantly stronger when applying the essential oil containing the compound of formula (I). Surprisingly, it was found that the perception of the individual precursor components (thiol, α,β-unsaturated carbonyl) was not simultaneous, the thiol component was perceived at 0 hours, bringing a stronger fruity character, while δ-damascone was perceived after 4-48 hours without any thiol notes being perceived.

[0364]

[0365]

[0366] Table 14: Average strength

[0367] Panelists were asked to describe the hedonic differences between the different samples.

[0368]

[0369]

[0370] Table 15: Panelists’ sensory descriptions

[0371]

[0372]

[0373] Table 16: Composition of essential oils used

[0374]

[0375]

[0376] Table 17: Composition of the deodorants used

[0377] 5. Shampoo

[0378] Aromatic shampoo samples were prepared by mixing appropriate amounts of the compound of formula (I) and DPG into essential oils and adding 1% of the resulting fragrance mixture to an unaromatized shampoo base.

[0379] Treat a slightly damp hair sample (2 g Caucasian hair) with 1 g of aromatized shampoo and wash thoroughly for 15 seconds. Then, let the sample stand for 30 seconds and rinse with warm water (30°C) for 15 seconds. Pass the sample between fingers to remove excess water.

[0380] The hair samples were dried on a clothesline and evaluated by 5 trained panelists after 0, 4 and 24 hours. Fragrance intensity was evaluated on a scale from no odor (0) to the strongest odor imaginable (9).

[0381]

[0382] Table 18: Average strength

[0383] Panelists were asked to describe the hedonic differences between the samples.

[0384]

[0385] Table 19: Panelists’ sensory descriptions

[0386]

[0387]

[0388] Table 20: Composition of essential oils used

[0389]

[0390] Table 21: Composition of the shampoo used

[0391] 6. Deodorant

[0392] Use synthetic skin (Vitro- The artificial skin model was prepared by using fat, cellulose and agar.

[0393] The aromatized deodorant samples were prepared by mixing the appropriate amount of precursor into the essential oil and adding 1% of the resulting fragrance mixture to the unaromatized deodorant base. 100 mg of the aromatized deodorant was applied to the artificial skin and spread evenly for 15 seconds. The models were then placed on a hot plate (43°C) and evaluated by 12 trained panelists after 0, 4, 24 and 48 hours. The fragrance intensity was evaluated on a scale from no odor (0) to the strongest odor imaginable (9).

[0394] It was detected that, at all evaluation stages, the perceived intensity of the essential oils containing the compound of formula (I) according to the invention was higher than that of the essential oils containing the precursor of the prior art (WO 2015 / 032885 A1), indicating a clear advantage of the compound of formula (I) according to the invention. Surprisingly, by introducing the pleasant smelling thiol component, both the hedonic characteristics and the perceived intensity of the fragrance after 0 hours were positively affected, while the excellent, long-lasting performance at 6-24 hours may be due to the lower evaporation characteristics / higher fragrance retention of the compound of formula (I) according to the invention.

[0395]

[0396]

[0397] Table 22: Most Intense Sample Probability

[0398]

[0399] Table 23: Average Strength

[0400]

[0401] Table 24: Most Intense Sample Probability

[0402]

[0403]

[0404] Table 25: Average Strength

[0405]

[0406]

[0407]

[0408] Table 26: Composition of essential oils used

[0409] 7. Fabric Softener

[0410] Aromatic fabric softener samples were prepared by mixing the appropriate amount of precursor into essential oils and adding 1% of the resulting fragrance mixture to unaromatized fabric softener.

[0411] 2 kg of cotton towels were washed in a European washing machine (Express 20 program, 20°C, 800 rpm) using 30 g of an aromatic fabric softener (the composition of the fabric softener is shown in Table 7). The fabrics were dried overnight on a clothesline and placed on a table for evaluation after 0 hours, 24 hours, 48 ​​hours, 72 hours and 144 hours. The fabrics were evaluated by 15 trained panelists. The fragrance intensity was evaluated on a scale from no odor (0) to the strongest odor imaginable (10). The panelists were also asked to select which sample had a higher perceived intensity.

[0412] It was detected that, at all evaluation stages, the perceived intensity of the essential oil containing the compound of formula (I) according to the invention was higher compared to the prior art precursor (WO 2015 / 032885 A1), indicating a clear advantage of the present system. Surprisingly, by introducing the pleasant smelling thiol component, both the hedonic characteristics and the perceived intensity of the fragrance after 0 hours were positively affected, while the excellent, long-lasting performance at 24-48 hours may be due to the lower evaporation characteristics / higher fragrance retention of the compound of formula (I) according to the invention.

[0413]

[0414]

[0415] Table 27: Most Intense Sample Probability

[0416]

[0417] Table 28: Average Strength

[0418]

[0419]

[0420] Table 29: Composition of essential oils used.

Claims

1. A compound of formula (I) (i) wherein R is selected from hydrogen and C 1 To C 10 The group consisting of a linear or cyclic alkyl residue, alkenyl residue or dienyl residue, preferably wherein the residue also carries one, two or more C 1 To C 4 a linear, cyclic or branched alkyl substituent, an alkenyl substituent or a diene substituent, and Wherein R' is selected from hydrogen and C 1 To C 10 The group consisting of linear or cyclic alkyl residues, alkenyl residues or diene residues, preferably, wherein the residues also carry one, two or more C 1 To C 4 a linear, cyclic or branched alkyl substituent, an alkenyl substituent or a diene substituent, and Where R 1 Selected from hydrogen and C 1 To C 10 The group consisting of a linear or cyclic alkyl residue, alkenyl residue or dienyl residue, preferably wherein the residue also carries one, two or more C 1 To C 4 a linear, cyclic or branched alkyl substituent, an alkenyl substituent or a diene substituent, and Where R 2 Choose from C 4 To C 15 The group consisting of a linear, cyclic or branched alkyl residue of Where R 3 Selected from hydrogen and C 1 To C 10 The group consisting of linear or cyclic alkyl residues, alkenyl residues or diene residues, preferably, wherein the residues also carry one, two or more C 1 To C 4 a straight-chain, cyclic or branched alkyl substituent, alkenyl substituent or diene substituent; or (ii) where R', R 2 and R 3 are independently selected from the groups defined in (i), and R and R 1 bonded together to form a saturated or unsaturated ring system containing 5 to 10 carbon atoms, preferably wherein the ring system further carries one, two or more C 1 To C 5 a linear, branched or cyclic alkyl substituent, alkenyl substituent or diene substituent; or (iii) where R', R 1 and R 2 are independently selected from the groups defined in (i), and R and R 3 bonded together to form a saturated or unsaturated monocyclic or bicyclic ring system containing 5 to 10 carbon atoms and optionally 1 or 2 ether functional groups, preferably wherein the ring system also carries one, two or more C 1 To C 5 A straight-chain, branched-chain or cyclic alkyl substituent, an alkenyl substituent or a diene substituent.

2. The compound of formula (I) according to claim 1, wherein R is selected from the group consisting of:

3. The compound of formula (I) according to claim 1 or 2, wherein R' is selected from the group consisting of:

4. A compound of formula (I) according to any one of the preceding claims, wherein R 1 Selected from the group consisting of:

5. A compound of formula (I) according to any one of the preceding claims, wherein R 2 Selected from the group consisting of:

6. A compound of formula (I) according to any one of the preceding claims, obtained or obtainable by a [1,4]-addition reaction between an α,β-unsaturated aldehyde or ketone and a thiol, The α,β-unsaturated aldehyde or ketone is selected from the group consisting of: The thiol is selected from the group consisting of:

7. A compound of formula (I) according to any one of the preceding claims, wherein the compound of formula (I) is selected from the group consisting of:

8. A fragrance mixture, preferably an essential oil, comprising or consisting of the following components composition: (i) one or more compounds of formula (I) according to any one of the preceding claims; and (ii) one or more other aromatic substances.

9. A method for producing a mixture of aromatic substances according to claim 8, preferably an essential oil, comprising the following steps or by the following steps composition: One or more compounds of formula (I) according to any one of claims 1 to 7 are mixed with one or more other aromatic substances.

10. A fragrance product comprising one or more compounds of formula (I) according to any one of claims 1 to 7 or a fragrance substance mixture according to claim 8, preferably an essential oil, preferably in an organoleptically effective amount.

11. The fragrance product of claim 10, wherein the product is selected from the group consisting of fragrance extracts; perfumes; eau de toilette; aftershave; cologne; pre-shave products; cologne sprays; scented cleansing cloths; acidic, alkaline and neutral detergents; textile fresheners; ironing aids; washing liquids; washing powders; clothing pretreaters; fabric softeners; washing soaps; washing tablets; disinfectants; surface disinfectants; air fresheners; aerosol sprays; waxes and polishes; personal care products; hand creams and lotions; foot creams and lotions; hair removal creams and lotions; aftershave creams and lotions; tanning creams and lotions; hair care products; deodorants and antiperspirants; decorative cosmetics; candles; lamp oils; incense sticks; insecticides; insect repellents; and fuels.

12. A method for producing a flavor product, preferably a method for producing a flavor product according to claim 10 or 11, the method comprising the following steps or consisting of the following steps composition: (i) providing one or more compounds of formula (I) according to any one of claims 1 to 7 or a fragrance substance mixture according to claim 8, preferably an essential oil; (ii) providing one or more other components of the flavor product to be produced; as well as (iii) contacting or mixing the other components provided in step (ii) with an organoleptically effective amount of the components provided in step (i).

13. Use of a compound of formula (I) according to any one of claims 1 to 7 as a precursor for releasing two or more different aromatic substances with pleasant odors, preferably, wherein the two or more different aromatic substances are released and / or sensory perceived at the same or different time points, preferably at different time points.

14. A method for releasing two or more different pleasant smells of aromatic substances, the method comprising the following steps or by the following steps composition: (a) providing a compound of formula (I) according to any one of claims 1 to 7, or a fragrance substance mixture according to claim 8, or a fragrance product according to claim 10 or 11, (b) optionally, applying or introducing the compound of formula (I) or the fragrance mixture or the fragrance product in step (a), preferably in an organoleptically effective amount, to the hair or skin or textile fibers or the surface to be perfumed, or to the ambient air to be perfumed, and (c) releasing two or more different pleasant-smelling fragrance substances from the compound of formula (I), preferably, wherein the two or more different pleasant-smelling fragrance substances are released and / or sensory perceived at the same or different time points, preferably at different time points.

15. A thiol selected from the group consisting of:

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