Precursors for the Controlled Release of α,β-Unsaturated Aldehydes or Ketones and Other Fragrance Substances with High Impact

Abstract

The present invention mainly relates to compounds of formula (I) as defined herein. The present invention also relates to a fragrance substance mixture as defined herein and a method for producing the same, a perfumed product as defined herein and a method for producing the same. The present invention further 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-smelling fragrance substances, a method for the release, two or more different pleasant-smelling fragrance substances, and 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 fragrance substance mixture as defined herein and a method for producing the same, a perfumed product as defined herein and a method for producing the same. The present invention further relates to the use of compounds of formula (I) as defined herein as precursors for the release of two or three or more different pleasant-smelling fragrance substances, a method for the release of two or three or more different pleasant-smelling fragrance substances, and thiols as defined herein. Further aspects and preferred embodiments of the present invention will become apparent from the following specification, the attached examples and, in particular, the attached claims.

Background Art

[0002] On the side of the fragrance industry, there is particular interest in the controlled and long-lasting release of specific fragrances. This is especially true for fragrances with high volatility or low persistence. For example, fabric washing is a field where it is highly desirable to be able to feel the pleasant aroma of fragrance substances or essential oils used in detergents or fabric softeners on the washed fabric over a long period after washing and drying.

[0003] Precursors are known in the fragrance industry and are formed, for example, via Michael addition from α,β-unsaturated carbonyl compounds and thiols. Precursors usually release pleasant-smelling α,β-unsaturated carbonyl compounds, such as α,β-unsaturated aldehydes or ketones. This release occurs in a controlled manner, thus enabling the sensory perception of highly volatile fragrance substances that would not be achievable if these aldehyde or ketone compounds were used directly in the essential oil.

[0004] In the fragrance industry, there is a strong demand for precursors that can release several fragrance substances simultaneously or over time. This would enable the expansion of the fragrance palette. There is also a particularly strong demand for fragrance substances that have a strong olfactory effect (i.e., a low olfactory threshold) even at low dosages, so-called "high-impact" fragrance substances.

[0005] Known precursors are limited to the release of fragrant α,β-unsaturated carbonyl compounds. Due to the unpleasant odor impression of common, especially short-chain thiol compounds, the prior art teaches the use of thiol compounds with as little fragrance as possible for the formation of precursors. For example, in Patent Document 1, 3-mercaptopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane are reacted with an α,β-unsaturated carbonyl compound to form a precursor. In the teachings described therein, only the released α,β-unsaturated carbonyl compound serves as a fragrance substance.

[0006] In Patent Document 2, short-chain thiol compounds are used as thiol compounds for the formation of precursors. Also in this published patent, only the α,β-unsaturated carbonyl compound released from the precursor serves as a fragrance substance. The unpleasant odor of the short-chain thiol compound also released from the precursor surprisingly does not have much of an adverse effect on the good olfactory effect of the α,β-unsaturated carbonyl compound, and thus it is described that, overall surprisingly, the good olfactory impression of the released α,β-unsaturated carbonyl compound predominates.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] The first problem was to provide an improved precursor that meets the above requirements, i.e., a fragrance that smells pleasant, has a large influence, and can be released in a controlled manner over a long period of time. This release should preferably be possible from surfaces treated with these precursors, especially from fabrics.

Means for Solving the Problems

[0009] Surprisingly, this problem is solved by formula (I):

[0010]

Chemical formula

[0011] (i) In the formula, R is selected from the group consisting of hydrogen and C1-C 10 , preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, linear or cyclic alkyl, alkenyl or alkadienyl residues, and preferably in the formula, these residues further have one, two, three, four or five or more C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and in the formula, these substituents may be the same or different from each other), and In the formula, R' is selected from the group consisting of hydrogen and C1-C 10 , preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, linear or cyclic alkyl, alkenyl or alkadienyl residues, and preferably in the formula, these residues further have one, two, three, four or five or more C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and in the formula, these substituents may be the same or different from each other), and In the formula, R 1 is hydrogen and C1-C10 and is preferably selected from the group consisting of linear or cyclic alkyl, alkenyl or alkadienyl residues having 1 to 9 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 7 carbon atoms, still more preferably 1 to 6 carbon atoms, and most preferably 1 to 5 carbon atoms. Preferably, in the formula, these residues further have one, two, three, four or more C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and in the formula, these substituents may be the same or different from each other), and wherein R 2 is C4-C 15 and is preferably C4-C 12 more preferably C5-C 12 more preferably C6-C 12 more preferably C7-C 12 and most preferably C8-C 12 selected from the group consisting of linear, cyclic or branched alkyl residues, preferably further containing one, two or more functional groups selected from the group consisting of ether, alcohol and ketone, more preferably further containing one ether group or two ether groups or one alcohol group or one ketone group, and wherein R 3 is hydrogen and C1-C 10 and is preferably selected from the group consisting of linear or cyclic alkyl, alkenyl or alkadienyl residues having 1 to 9 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 7 carbon atoms, still more preferably 1 to 6 carbon atoms, and most preferably 1 to 5 carbon atoms. Preferably, in the formula, these residues further have one, two, three, four or more C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and in the formula, these substituents may be the same or different from each other), or (ii) wherein R′, R 2 and R 3 are each independently selected from the group defined in (i), and R and R 1is joined together to form a saturated or unsaturated ring system containing 5 to 10 carbon atoms, preferably 6 to 8 carbon atoms, and most preferably 6 carbon atoms. Preferably, in the formula, this ring system further has one, two, three, four or five or more C1-C5 linear, branched or cyclic alkyl, alkenyl or alkadienyl substituents (and in the formula, these substituents may be the same as or different from each other), alternatively, (iii) in the formula, R′, R 1 and R 2 are each independently selected from the group defined in (i), and R and R 3 is joined together to form a saturated or unsaturated, monocyclic or bicyclic ring system containing 5 to 10 carbon atoms and optionally one or two ether functional groups, preferably 6 to 8 carbon atoms and optionally one ether functional group, and most preferably 6 carbon atoms. Preferably, in the formula, this ring system further has one, two, three, four or five or more C1-C5 linear, branched or cyclic alkyl, alkenyl or alkadienyl substituents, preferably one, two or three or more methyl groups, is solved by the compound of

[0012] The ring system defined in (ii) above contains the carbon atom to which R and R 1 are attached, and the ring system defined in (iii) above contains the carbon atom to which R and R 3 are attached.

[0013] The compound of formula (I) (i.e., this precursor) may be in the form of a pure diastereomer or stereoisomer or any mixture of said isomers.

Advantages of the Invention

[0014] The compounds of formula (I) as defined herein have not been known hitherto in the fragrance industry. Thus, the suitability of the compounds of formula (I) as precursors for the release of fragrance substances was unexpected. During the course of the investigations underlying the present application, and contrary to the teachings in the prior art regarding the adverse olfactory effects of the thiol compounds released, surprisingly, the compounds of formula (I) according to the invention were found to release both a pleasantly fragrant (high-impact) α,β-unsaturated aldehyde or ketone and a pleasantly fragrant (high-impact) thiol compound. The release of these two (or more than two) different fragrance substances, and thus their sensory perception, advantageously occurs in a controlled manner, preferably at different times, which was particularly surprising. For example, the sensory aroma impression of the thiol compound released (e.g., sulfurous notes to fruity notes) is very strongly recognizable, especially in freshly laundered, damp laundry, while the α,β-unsaturated aldehyde or ketone released provides a long-lasting, fresh aroma impression (e.g., fresh notes, green notes and / or flowery notes) in dry laundry.

[0015] Further advantages of the present invention are as follows. - Due to the controlled release of two different pleasantly fragrant, high-impact fragrance substances with low fragrance thresholds (α,β-unsaturated aldehyde or ketone compounds, thiol compounds), a distinct aroma perception occurs even when small amounts of the compounds of formula (I) according to the invention are used. - Surprisingly, since both compounds released by the compounds of formula (I) according to the invention (α,β-unsaturated aldehyde or ketone compounds, thiol compounds) contribute to a pleasant aroma profile, a higher atom economy is achieved compared to the precursors of the prior art. - These different fragrance substances are preferably released from the compounds of formula (I) according to the invention and / or are sensorially perceived at different times, so that surprisingly, the beneficial effect of the compounds of formula (I) according to the invention on the fragrance impression is achieved both in wet laundry (thiol compounds) and in dry laundry (α,β-unsaturated aldehyde or ketone compounds). - The thiol compounds released by the compounds of formula (I) according to the invention not only improve the persistence and / or deposition of the compounds of formula (I) according to the invention on, for example, fabrics, hair or skin, but also serve as fragranced substances that are pleasantly fragrant in themselves.

Brief Description of the Drawings

[0016]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0017] According to a preferred embodiment of the compounds of formula (I) according to the invention, R is hydrogen and C1-C 10 , preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, selected from the group consisting of linear or cyclic alkyl or alkenyl residues, and preferably these residues further have one, two, three, four or more C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and these substituents may be the same or different from each other), and R′ is hydrogen and C1-C 10 , preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, selected from the group consisting of linear or cyclic alkyl or alkenyl residues, and preferably, these residues further have one, two, three, four or more than five C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and these substituents may be the same or different from each other), and R 1 is hydrogen and C1-C 10 , preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, selected from the group consisting of linear or cyclic alkyl or alkenyl residues, and preferably, these residues further have one, two, three, four or more than five C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and these substituents may be the same or different from each other), and R 2 is C6-C 12 , more preferably C7-C 12 , most preferably C8-C 12 selected from the group consisting of linear, cyclic or branched alkyl residues, and preferably further contains one, two or more than three functional groups selected from the group consisting of ether, alcohol and ketone, more preferably further contains one ether group or two ether groups or one alcohol group or one ketone group, and R 3 is hydrogen and C1-C 10, preferably C1-C9, more preferably C1-C8, still more preferably C1-C7, even more preferably C1-C6, most preferably C1-C5, selected from the group consisting of linear or cyclic alkyl or alkenyl residues, preferably, these residues further have one, two, three, four or more C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and these substituents may be the same or different from each other).

[0018] According to another preferred embodiment of the compound of formula (I) according to the present invention, R is hydrogen and C1-C 10 , preferably C1-C9, more preferably C1-C8, still more preferably C1-C7, even more preferably C1-C6, most preferably C1-C5, selected from the group consisting of linear or cyclic alkyl or alkenyl residues, preferably, these residues further have one, two, three or four or more substituents selected from the group consisting of methyl and ethenyl (and these substituents may be the same or different from each other), and R' is hydrogen and C1-C 10 , preferably C1-C9, more preferably C1-C8, still more preferably C1-C7, even more preferably C1-C6, most preferably C1-C5, selected from the group consisting of linear or cyclic alkyl or alkenyl residues, preferably, these residues further have one, two, three or four or more substituents selected from the group consisting of methyl and ethenyl (and these substituents may be the same or different from each other), and R 1 is hydrogen and C1-C 10 , preferably C1-C9, more preferably C1-C8, still more preferably C1-C7, even more preferably C1-C6, most preferably C1-C5, selected from the group consisting of linear or cyclic alkyl or alkenyl residues, preferably, these residues further have one, two, three or four or more substituents selected from the group consisting of methyl and ethenyl (and these substituents may be the same or different), and R 2 is a straight-chain, cyclic or branched alkyl residue selected from the group consisting of C6-C 12 , more preferably C7-C 12 , most preferably C8-C 12 , and preferably further contains one, two or more functional groups selected from the group consisting of ether, alcohol and ketone, more preferably further contains one ether group or two ether groups or one alcohol group or one ketone group, and R 3 is selected from the group consisting of hydrogen and straight-chain or cyclic alkyl or alkenyl residues of C1-C 10 , preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, and preferably these residues further have one, two, three or more substituents selected from the group consisting of methyl and ethenyl (and these substituents may be the same or different from each other).

[0019] According to another preferred embodiment of the compound of formula (I) according to the present invention, R is selected from the group consisting of hydrogen and straight-chain or cyclic alkyl or alkenyl residues of C1-C 10 , preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, and preferably these residues further contain one, two, three or more substituents selected from the group consisting of methyl and ethenyl (and these substituents may be the same or different from each other), and R′ is hydrogen and C1-C 10, preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, selected from the group consisting of linear or cyclic alkyl or alkenyl residues, preferably these residues further contain one, two, three or more substituents selected from the group consisting of methyl and ethenyl (and these substituents may be the same or different from each other), and R 1 is hydrogen and C1-C 10 , preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, selected from the group consisting of linear or cyclic alkyl or alkenyl residues, preferably these residues further contain one, two, three or more substituents selected from the group consisting of methyl and ethenyl (and these substituents may be the same or different from each other), R 2 is C6-C 12 , more preferably C7-C 12 , most preferably C8-C 12 selected from the group consisting of linear, cyclic or branched alkyl residues, preferably further contains one, two or more functional groups selected from the group consisting of ether, alcohol and ketone, more preferably further contains one ether group or two ether groups or one alcohol group or one ketone group, R 3 is hydrogen.

[0020] The residue R of the compound of formula (I) according to the present invention 2 does not contain any Si atoms.

[0021] According to another preferred embodiment of the compound of formula (I) according to the present invention, R 2 is not an n-butyl, n-pentyl or n-hexyl (or 2-propyl) residue.

[0022] According to another preferred embodiment of the compound of formula (I) according to the present invention, R2 is not the residue (4-hydroxybutyl) of the following formula,

[0023]

Chemical formula

[0024] .

[0025] According to a preferred alternative embodiment of the compound of formula (I) according to the present invention, R 2 is selected from the group consisting of linear, cyclic or branched alkyl residues of C4-C 15 , preferably C4-C 12 , more preferably C5-C 12 , more preferably C6-C 12 , more preferably C7-C 12 , most preferably C8-C 12 and further contains one, two or more ether functional groups.

[0026] According to a preferred alternative embodiment of the compound of formula (I) according to the present invention, R 2 is selected from the group consisting of linear, cyclic or branched alkyl residues of C4-C 15 , preferably C4-C 12 , more preferably C5-C 12 , more preferably C6-C 12 , more preferably C7-C 12 , most preferably C8-C 12 and further contains one ether functional group.

[0027] According to a preferred alternative embodiment of the compound of formula (I) according to the present invention, R 2 is selected from the group consisting of linear, cyclic or branched alkyl residues of C4-C 15 , preferably C4-C 12 , more preferably C5-C 12 , more preferably C6-C 12 , more preferably C7-C 12 , most preferably C8-C 12 and further contains two ether functional groups.

[0028] According to a preferred alternative embodiment of the compound of formula (I) according to the present invention, R 2 is a straight-chain, cyclic or branched alkyl residue selected from the group consisting of C4-C 15 , preferably C4-C 12 , more preferably C5-C 12 , more preferably C6-C 12 , more preferably C7-C 12 , most preferably C8-C 12 and further contains one, two or more alcohol functional groups.

[0029] According to a preferred alternative embodiment of the compound of formula (I) according to the present invention, R 2 is a straight-chain, cyclic or branched alkyl residue selected from the group consisting of C4-C 15 , preferably C4-C 12 , more preferably C5-C 12 , more preferably C6-C 12 , more preferably C7-C 12 , most preferably C8-C 12 and further contains one alcohol functional group.

[0030] According to a preferred alternative embodiment of the compound of formula (I) according to the present invention, R 2 is a straight-chain, cyclic or branched alkyl residue selected from the group consisting of C4-C 15 , preferably C4-C 12 , more preferably C5-C 12 , more preferably C6-C 12 , more preferably C7-C 12 , most preferably C8-C 12 and further contains two alcohol functional groups.

[0031] According to a preferred alternative embodiment of the compound of formula (I) according to the present invention, R 2 is a straight-chain, cyclic or branched alkyl residue selected from the group consisting of C4-C 15 , preferably C4-C 12 , more preferably C5-C 12 , more preferably C6-C12 and more preferably C7-C 12 and most preferably C8-C 12 selected from the group consisting of linear, cyclic or branched alkyl residues, and further containing one, two or more ketone functional groups.

[0032] According to a preferred alternative embodiment of the compound of formula (I) according to the present invention, R 2 is C4-C 15 preferably C4-C 12 more preferably C5-C 12 more preferably C6-C 12 more preferably C7-C 12 and most preferably C8-C 12 selected from the group consisting of linear, cyclic or branched alkyl residues, and further containing one ketone functional group.

[0033] According to a preferred alternative embodiment of the compound of formula (I) according to the present invention, R 2 is C4-C 15 preferably C4-C 12 more preferably C5-C 12 more preferably C6-C 12 more preferably C7-C 12 and most preferably C8-C 12 selected from the group consisting of linear, cyclic or branched alkyl residues, and further containing two ketone functional groups.

[0034] According to a preferred embodiment of the compound of formula (I) according to the present invention, R is

[0035]

Chemical formula

[0036] selected from the group consisting of.

[0037] According to another preferred embodiment of the compound of formula (I) according to the present invention, R' is

[0038] [Chemical formula]

[0039] selected from the group consisting of.

[0040] According to another preferred embodiment of the compound of formula (I) according to the present invention, R 1 is

[0041] [Chemical formula]

[0042] selected from the group consisting of.

[0043] According to another preferred embodiment of the compound of formula (I) according to the invention, R 2 is

[0044] [Chemical formula] [Chemical formula]

[0045] selected from the group consisting of.

[0046] According to another preferred embodiment of the compound of formula (I) according to the invention, R 2 is

[0047] [Chemical formula] [Chemical formula]

[0048] selected from the group consisting of.

[0049] According to another preferred embodiment of the compound of formula (I) according to the present invention, R is hydrogen and C1-C10 and preferably selected from the group consisting of linear or cyclic alkyl, alkenyl or alkadienyl residues of C1-C9, more preferably C1-C8, even more preferably C1-C7, even more preferably C1-C6, and most preferably C1-C5, and preferably, these residues further contain one, two, three, four or more C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and these substituents may be the same or different from each other), and R′ is hydrogen and C1-C 10 and preferably selected from the group consisting of linear or cyclic alkyl, alkenyl or alkadienyl residues of C1-C9, more preferably C1-C8, even more preferably C1-C7, even more preferably C1-C6, and most preferably C1-C5, and preferably, these residues further contain one, two, three, four or more C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and these substituents may be the same or different from each other), and R 1 is hydrogen and C1-C 10 and preferably selected from the group consisting of linear or cyclic alkyl, alkenyl or alkadienyl residues of C1-C9, more preferably C1-C8, even more preferably C1-C7, even more preferably C1-C6, and most preferably C1-C5, and preferably, these residues further contain one, two, three, four or more C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and these substituents may be the same or different from each other), and R 2 is of the following formula

[0050]

Chemical formula

Chemical formula

[0051] selected from the group consisting of, and R 3 is hydrogen and C1-C 10 , preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, a linear or cyclic alkyl, alkenyl or alkadienyl residue selected from the group consisting of, preferably, these residues further have one, two, three, four or more than five C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and these substituents may be the same or different from each other).

[0052] According to a particularly preferred embodiment of the compound of formula (I) according to the present invention, R is hydrogen and C1-C 10 , preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, a linear or cyclic alkyl, alkenyl or alkadienyl residue selected from the group consisting of, preferably, these residues further have one, two, three, four or more than five C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and these substituents may be the same or different from each other), and R′ is hydrogen and C1-C 10 , preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, a linear or cyclic alkyl, alkenyl or alkadienyl residue selected from the group consisting of, preferably, these residues further contain one, two, three, four or more than five C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and these substituents may be the same or different from each other), and R 1 is hydrogen and C1-C 10, preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, selected from the group consisting of linear or cyclic alkyl, alkenyl or alkadienyl residues, preferably these residues further have one, two, three, four or more than five C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and these substituents may be the same or different from each other), and R 2 is

[0053] [Chemical formula] [Chemical formula]

[0054] selected from the group consisting of, and R 3 is hydrogen and C1-C 10 , preferably C1-C9, more preferably C1-C8, more preferably C1-C7, more preferably C1-C6, most preferably C1-C5, selected from the group consisting of linear or cyclic alkyl, alkenyl or alkadienyl residues, preferably these residues further have one, two, three, four or more than five C1-C4 linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents (and these substituents may be the same or different from each other).

[0055] According to another particularly preferred embodiment of the compound of formula (I) according to the present invention, the residue of the compound of formula (I)

[0056] [Chemical formula]

[0057] is

[0058] [Chemical formula]

Chem.

Chem.

[0059] selected from the group consisting of and / or, preferably and, the residue R of the compound of formula (I) 2 is

[0060]

Chem.

Chem.

[0061] selected from the group consisting of.

[0062] According to a preferred embodiment, the compound of formula (I) according to the present invention is -(the group of compounds shown in the column entitled "Structure" in Table 1 below)

[0063]

Table 1-1

Table 1-2

Table 1-3

Table 1-4

Table 1-5

[0064] an α,β-unsaturated aldehyde or ketone (Michael acceptor, electrophilic reagent) selected from the group consisting of, and -(the group of compounds shown in the column titled "Structure" in Table 2 below)

[0065]

Table 2-1

Table 2-2

Table 2-3

Table 2-4

[0066] a thiol (Michael donor, nucleophile) selected from the group consisting of obtained or obtainable by a [1,4]-addition reaction between

[0067] According to a preferred embodiment, citral - a mixture of neral and geranial as shown in Table 1 above - is used as the α,β-unsaturated aldehyde (mixture) for the formation of the compound of formula (I).

[0068] The compound of formula (I) according to the present invention

[0069]

Chemical formula

[0070] is of the following formula

[0071]

Chemical formula

[0072] By the decomposition reaction, a (pleasantly fragrant, highly influential) thiol preferably selected from the group consisting of the compounds shown in the column entitled "Structure" in Table 2 above, and a (pleasantly fragrant, highly influential) α,β-unsaturated aldehyde or ketone preferably selected from the group consisting of the compounds shown in the column entitled "Structure" in Table 1 above are released.

[0073] Preferably, the release is caused by a specific pH value and / or temperature, ultraviolet light, moisture, and / or oxygen.

[0074] According to a particularly preferred embodiment, the compound of formula (I) according to the invention is (the group of compounds shown in the column entitled "Structure" in Table 3 below)

[0075]

Table 3-1

Table 3-2

Table 3-3

Table 3-4

Table 3-5

Table 3-6

Table 3-7

Table 3-8

Table 3-9

Table 3-10

Table 3-11

[0076] selected from the group consisting of

[0077] According to a particularly preferred embodiment, the compound of formula (I) according to the invention is

[0078]

Chemical formula

[0079] not.

[0080] Another aspect of the invention relates to a fragrance material mixture comprising or consisting of the following components, (i) one or more compounds of formula (I) as defined herein, and (ii) one or more further fragrance materials, preferably relating to an essential oil.

[0081] These one or more further fragrance materials are different from the compounds of formula (I) according to the invention.

[0082] Examples of further fragrance materials that can be advantageously combined within the scope of the invention with the compounds of formula (I) as defined herein are known to those skilled in the art and can be found, for example, in S. Arctander, Perfume and Flavor Materials, Volumes I and II, Montclair, N.J. 1969, Eigenverlag or K. Bauer et al., Common Fragrance and Flavor Materials, 4th Edition, Wiley-VCH, Weinheim, 2001.

[0083] According to a preferred embodiment of the fragrance substance mixture, preferably perfume oil, according to the invention, the proportion of the total amount of the compound of formula (I) as defined herein in the fragrance substance mixture is 0.1 to 3% by weight, preferably 0.5 to 2.5% by weight, particularly preferably 1 to 2% by weight, based on the total mass of the fragrance substance mixture.

[0084] Another aspect of the invention relates to a method for producing the fragrance substance mixture, preferably perfume oil, as defined above, which comprises or consists of the following steps.

[0085] Mixing one or more compounds of formula (I) as defined herein with one or more further fragrance substances.

[0086] Furthermore, the fragrance substance mixture according to the invention, preferably perfume oil, may be adsorbed on a carrier which provides both a fine distribution of the fragrance substance mixture, preferably perfume oil, in the perfume product and a controlled release upon application. Such carriers may be porous inorganic materials such as light sulfate, silica gel, zeolite, gypsum, clay, clay granules, cellular concrete, etc. or organic materials such as wood, cellulose-based materials, sugar, dextrin (e.g. maltodextrin) or plastics such as PVC, polyvinyl acetate or polyurethane. The combination of the fragrance substance mixture according to the invention, preferably perfume oil, and the carrier should also be understood as the fragrance substance mixture according to the invention, preferably perfume oil, or may be presented as a perfume product according to the invention (described below).

[0087] (The fragrance substance mixture according to the invention, preferably perfume oil, or perfume product described below) may also be microencapsulated, spray-dried, or provided as an inclusion complex or an extruded product, and in the case of the fragrance substance mixture, preferably perfume oil, may be added in this form, for example, to a perfume product to be perfumed (described below).

[0088] If necessary, the properties of such a modified mixture or product can be further optimized, with a view to improving the targeted release of the fragrance, by means of a so-called "coating" with a suitable material, preferably a waxy plastic such as polyvinyl alcohol. The resulting product then represents the product of the invention.

[0089] For example, microencapsulation can be achieved by means of the so-called coacervation method using a capsule material such as a polyurethane-like material or soft gelatin.

[0090] Spray-dried products are preferably produced by spray-drying an emulsion or dispersion containing a fragrance substance mixture according to the invention, preferably an essential oil, and in this case, modified starch, protein, dextrin and vegetable gums can be used as carriers.

[0091] The inclusion complex can be produced, for example, by incorporating a dispersion of a fragrance substance mixture according to the invention, preferably an essential oil, and cyclodextrin or a urea derivative into a suitable solvent, for example water.

[0092] For example, an extruded product can be obtained by using a fragrance substance mixture according to the invention, preferably an essential oil, and a suitable wax substance, and extrusion and, if necessary, subsequent solidification in a suitable solvent, for example isopropanol.

[0093] Another aspect of the invention relates to a perfumed product containing one or more compounds of formula (I) as defined herein, or a fragrance substance mixture as defined herein, preferably an essential oil, preferably in a sensually effective amount.

[0094] Advantageously, this one or more compounds of formula (I) according to the invention impart or modify the fragrance of the perfumed product to which the said compound of formula (I) is added in a favorable direction.

[0095] According to a preferred embodiment, the perfumed product is selected from the group consisting of perfume extracts, eau de parfum, eau de toilette, aftershave, eau de cologne, pre-shave products, splash cologne, perfumed refreshing cloths, acidic, alkaline and neutral detergents, fabric fresheners, ironing aids, liquid detergents, powder detergents, laundry pre-treatments, fabric softeners, laundry soaps, laundry tablets, bactericides, surface bactericides, 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, shaving creams and lotions, hair care products, deodorants and antiperspirants, decorative cosmetic products, candles, lamp oils, perfume sticks, insecticides, insect repellents and fuels, and most preferably a fabric softener.

[0096] According to a preferred embodiment of the perfumed product according to the invention, the proportion of the fragrance substance mixture as defined herein, preferably the total amount of the perfume oil, in the perfumed product is 0.1 to 3% by weight, preferably 0.5 to 2.5% by weight, particularly preferably 1 to 2% by weight, based on the total mass of the perfumed product.

[0097] Another aspect of the invention is a method for manufacturing a perfumed product, preferably a perfumed product as defined herein, comprising the following (i) providing one or more compounds of formula (I) as defined herein or a fragrance substance mixture as defined herein, preferably a perfume oil; (ii) providing one or more further components of the perfumed product to be manufactured; and (iii) contacting or mixing the further components provided in step (ii) with a sensibly effective amount of the components provided in step (i). The invention relates to a method comprising these steps.

[0098] Another aspect of the present invention is the use of a compound of formula (I) as defined herein as a precursor for the (controlled) release of one, two, three or more than four different fragrance substances having a pleasant smell, preferably, when two or more different fragrance substances are released, they are released at the same or different, preferably different times and / or are sensed, related to the use.

[0099] Another aspect of the present invention is the use of a compound of formula (I) as defined herein as a precursor for the (controlled) release of a thiol having a pleasant smell and an α,β-unsaturated aldehyde or ketone having a pleasant smell, preferably, the thiol and the α,β-unsaturated aldehyde or ketone are released at the same or different, preferably different times and / or are sensed, related to the use.

[0100] Another aspect of the present invention is

[0101]

Chemical formula

Chemical formula

Chemical formula

[0102] of a thiol selected from the group consisting of (having a pleasant smell) and / or, preferably and

[0103]

Chemical formula

Chemical formula

Chemical formula

[0104] Use of a compound of formula (I) as defined herein as a precursor for the (controlled) release of an (olfactorily pleasing) α,β-unsaturated aldehyde or ketone selected from the group consisting of, preferably, the thiol and the α,β-unsaturated aldehyde or ketone being released and / or sensed at the same or different, preferably different, times.

[0105] Another aspect of the invention is the use of a compound of formula (I), wherein the residue of the compound of formula (I)

[0106]

Chemical formula

[0107] is

[0108]

Chemical formula

Chemical formula

Chemical formula

[0109] selected from the group consisting of and / or, preferably and, the residue R of the compound of formula (I) 2 is

[0110]

Chemical formula

Chemical formula

[0111] selected from the group consisting of

[0112]

Chemical formula

[0113] of a (pleasantly fragrant) thiol selected from the group consisting of, and / or, preferably and,

[0114] [Chemistry] [Chemistry] [Chemistry]

[0115] Use of a compound of formula (I) as a precursor for the (controlled) release of a (pleasantly fragrant) α,β-unsaturated aldehyde or ketone selected from the group consisting of, wherein preferably, the thiol and the α,β-unsaturated aldehyde or ketone are released and / or sensed at the same or different, preferably different, times.

[0116] The thiols and α,β-unsaturated aldehydes or ketones released by the compounds of formula (I) according to the invention and / or used for the formation of the compounds of formula (I) according to the invention may be in the form of pure diastereomers or stereoisomers or any mixture of said isomers.

[0117] 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 sensed before the α,β-unsaturated aldehyde or ketone released from the (same) compound of formula (I) as defined herein.

[0118] 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 before and / or is sensed more readily than the thiol released from the (same) compound of formula (I) as defined herein.

[0119] 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 simultaneously and / or are sensed more readily.

[0120] Preferably, the pleasantly fragrant thiol has one or more aroma notes selected from the group consisting of grapefruit, cassis, onion, fruity, exotic fruit, guava, smoker's breath, sulfur, (burnt) plastic, (minty) green, rose oxide, green pepper, liver sausage, bukko (Asian chive), gasoline, juicy, natural, catnip, meat broth (''Fleischbruehe''), cheesy, camembert, cheese in the refrigerator, fresh, hot rubber, gasoline, violet, crofusasugri, dog fennel (grass), zestral, anise-like, mushroom, soup, spring onion, agrumen, peach, meat, pine, mango, durian, parmitz, artichoke and apricot. More preferably, the thiols that smell pleasant are selected from the group consisting of one or more fragrance notes from grapefruit, cassis, onion, fruity, exotic fruit, guava, sulfur, (minty) green, rose oxide, green pepper, liver sausage, bukko (Asian chive), juicy, natural, catnip, meat broth (flesh bouillon), cheesy, camembert, fresh, violet, croftsus green, dog grass (grass), zestral, anise-like, mushroom, soup, welsh onion, agrumen, peach, meat, pine, mango, durian, parmitz, artichoke, and apricot.

[0121] Another aspect of the present invention is the following (a) providing a compound of formula (I) as defined herein or a fragrance substance mixture as defined herein (comprising one or more compounds of formula (I) as defined herein) or a perfumed product as defined herein (comprising one or more compounds of formula (I) as defined herein); (b) optionally, applying or introducing the compound of formula (I) or the fragrance substance mixture or the perfumed product of step (a), preferably in a sensorially effective amount, to hair or skin or fabric fibers or to a surface to be perfumed or into the ambient air to be perfumed; (c) releasing one, two, three or more different pleasant-smelling fragrance substances from the compound of formula (I), preferably wherein two or more of these different pleasant-smelling fragrance substances are released at the same or different, preferably different, times and / or are sensorially recognized (when two or more different fragrance substances are released); relates to a method for the (controlled) release of one, two, three or more different pleasant-smelling fragrance substances, comprising or consisting of

[0122] Another aspect of the present invention is the following (a) A step of providing a compound of formula (I) as defined herein or a fragrance substance mixture as defined herein (comprising one or more compounds of formula (I) as defined herein) or a perfumed product as defined herein (comprising one or more compounds of formula (I) as defined herein). (b) Optionally, a step of applying or introducing the compound of formula (I) or the fragrance substance mixture or the perfumed product of step (a), preferably in a sensorially effective amount, to hair or skin or fabric fibers or to a surface to be perfumed or into the ambient air to be perfumed. (c) A step of releasing a pleasantly fragrant thiol and a pleasantly fragrant α,β-unsaturated aldehyde or ketone from the compound of formula (I), preferably, the pleasantly fragrant thiol and the pleasantly fragrant α,β-unsaturated aldehyde or ketone are released at the same or different, preferably different times and / or are sensorially recognized. Relates to a method for the (controlled) release of a pleasantly fragrant thiol and a pleasantly fragrant α,β-unsaturated aldehyde or ketone, comprising or consisting of.

[0123] According to a preferred embodiment of the method according to the invention, the thiol released from the compound of formula (I) as defined herein in step (c) is released before and / or is sensorially recognized before the α,β-unsaturated aldehyde or ketone released from the (same) compound of formula (I) as defined herein in step (c).

[0124] According to an alternative embodiment of the method according to the invention, the α,β-unsaturated aldehyde or ketone released from the compound of formula (I) as defined herein in step (c) is released before and / or is sensorially recognized before the thiol released from the (same) compound of formula (I) as defined herein in step (c).

[0125] According to a further alternative embodiment of the method according to the 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 simultaneously and / or are perceived sensorially.

[0126] Another aspect of the invention is

[0127]

Chemical formula

Chemical formula

Chemical formula

[0128] of a (pleasantly fragrant) thiol selected from the group consisting of, and / or, preferably and,

[0129]

Chemical formula

Chemical formula

Chemical formula

[0130] a method for the (controlled) release of a (pleasantly fragrant) α,β-unsaturated aldehyde or ketone selected from the group consisting of, comprising the following, (a) providing a compound of formula (I) (or a fragrance substance mixture or a perfumed product comprising a compound of formula (I) as defined above), wherein the residue of the compound of formula (I)

[0131]

Chemical formula

[0132] is

[0133] [Chem.] [Chem.] [Chem.]

[0134] selected from the group consisting of and / or, preferably and, the residue R of the compound of formula (I) 2 is

[0135] [Chem.] [Chem.]

[0136] a step selected from the group consisting of (b) Optionally, the compound of formula (I) in step (a) (or a fragrance substance mixture or a perfumed product containing the compound of formula (I) in step (a)) is preferably applied or introduced in a sensibly effective amount to hair or skin or cloth fibers or to a surface to be perfumed or into the perfumed ambient air (c) A step of releasing a thiol and / or an α,β-unsaturated aldehyde or ketone (which smells pleasant) from the compound of formula (I), preferably, the thiol (which smells pleasant) and the α,β-unsaturated aldehyde or ketone (which smells pleasant) are released at the same or different, preferably different points in time and / or are sensed relates to a method comprising

[0137] Another aspect of the present invention is

[0138] [Chem.]

Chem.

[0139] relates to a thiol selected from the group consisting of.

[0140] Surprisingly, during the studies underlying the present invention, it has been found that the thiols defined above can, after release from the compounds of formula (I) according to the invention, preferably serve as highly fragrant and powerful fragrances.

[0141] The thiols according to the invention can be obtained by applying the procedure disclosed in WO 2019 / 037862 (A1).

[0142] The olfactory descriptions of the thiols according to the invention can be found in Table 2 above.

[0143] Accordingly, another aspect of the invention relates to the use of one or more thiols according to the invention as fragrance substances.

[0144] Another aspect of the invention is as follows (a) (i) one or more thiols defined herein and preferably also a surfactant or surfactant mixture, or (ii) one or more compounds of formula (I) defined herein and preferably also a surfactant or surfactant mixture, or (iii) a fragrance substance mixture defined herein containing preferably a surfactant or surfactant mixture, or (iv) a perfumed product defined herein containing preferably a surfactant or surfactant mixture, providing step, and (b)(i) The thiol and preferably the surfactant or surfactant mixture, or (ii) the compound and preferably the surfactant or surfactant mixture, or the fragrance substance mixture of (ii) or the perfumed product of (iii) in step (a) are applied or introduced in a sensibly effective amount to the hair or skin or fabric fiber or to the surface to be perfumed or into the perfumed ambient air, and relates to a method for perfuming hair, skin, fabric fiber, surface and / or ambient air, comprising or consisting of.

[0145] Another aspect of the present invention relates to the use of a compound of formula (I) as defined herein, or of a fragrance substance mixture as defined herein, preferably an essential oil, as a perfuming ingredient.

[0146] Another aspect of the present invention relates to the use of a compound of formula (I) as defined herein, or of a fragrance substance mixture as defined herein, preferably an essential oil, for perfuming hair, skin, fabric fiber, surface and / or ambient air.

[0147] Another aspect of the present invention relates to a fragrance substance mixture as defined herein, preferably an essential oil, wherein the amount of the compound of formula (I) is (a) sufficient to mask or reduce the unpleasant odor impression of one or several other fragrance substances in the fragrance substance mixture, and / or and / or (b) sufficient to enhance the pleasant fragrance impression of one or several other fragrance substances in the fragrance substance mixture. relates to a fragrance substance mixture, preferably an essential oil, which is sufficient.

[0148] Another aspect of the present invention is (a) for masking or reducing this unpleasant odor impression of one or several kinds of malodorous substances or one or several kinds of unpleasant odor impressions, and / or and / or (b) For enhancing this pleasant fragrance impression of one or several types of pleasant-smelling substances or one or several types of pleasant fragrance impressions, Regarding the use of one or two or more compounds of formula (I) as defined herein, or a fragrance substance mixture as defined herein, preferably an essential oil.

[0149] Another aspect of the present invention is (a) For masking or reducing this unpleasant odor impression of one or several types of unpleasant-smelling substances or one or several types of unpleasant odor impressions, And / or (b) For enhancing this pleasant fragrance impression of one or several types of pleasant-smelling substances or one or several types of pleasant fragrance impressions, Regarding a method, which includes the following steps.

[0150] A step of mixing an unpleasant-smelling substance and / or a pleasant-smelling substance with one or two or more compounds of formula (I) as defined herein, or a fragrance substance mixture as defined herein, preferably an essential oil, wherein the amount of one or two or more compounds of formula (I) as defined herein, or the fragrance substance mixture as defined herein, preferably the essential oil, is sufficient to (a) reduce or mask the unpleasant odor impression of the unpleasant-smelling substance, and / or (b) enhance the pleasant fragrance impression of the pleasant-smelling substance.

[0151] What has been described herein in connection with the fragrance substance mixture, the perfumed product, the method, the use, and the thiol according to the present invention applies mutatis mutandis to the preferred embodiments of the compounds of formula (I) according to the present invention, and vice versa.

[0152] Hereinafter, the present invention will be described in more detail with reference to examples.

Examples

[0153] Synthesis procedure of the precursor according to the present invention

[0154] 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)

[0155]

Chemical formula

[0156] 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 to a 500 ml stirring apparatus equipped with a magnetic stirring device, a reflux condenser, a thermometer, a dropping funnel and an ice bath at 0 °C under a nitrogen atmosphere. 8.1 g of δ-damascone was added dropwise over 1 hour at 0 - 5 °C. Stirring was continued for 6 hours at 0 - 5 °C for the post-reaction. The mixture was washed twice with saturated sodium bicarbonate solution at room temperature, and then the solvent was evaporated using a rotary evaporator. 16.8 g of a crude product of 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyl-1-(2,6,6-trimethyl-cyclohex-3-en-1-yl)butan-1-one having a 90% GC content was obtained. For further purification, this crude product was separated by chromatography on a silica gel column using hexane:diethyl ether (10:1) as the eluent. 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 having a 94% GC content was obtained. Mass spectrometry of the product m / z: 99 (100), 123 (35), 81 (35), 43 (33), 69 (27), 115 (24), 55 (18), 225 (17), 41 (17), 192 (16)

[0157] 2. Synthesis of the precursor 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyldecanal (compound of formula (I) according to the present invention)

[0158] [Chemical formula]

[0159] 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 in a 500 ml stirring device equipped with a magnetic stirrer, reflux condenser, thermometer, dropping funnel and ice bath at 0 °C under a nitrogen atmosphere. 6.4 g of 2-(E)decanal was added dropwise over 1 hour at 0 - 5 °C. For the post-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 using a rotary evaporator. 14.6 g of a crude product of 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyldecanal with a GC content of 76% was obtained. For further purification, this crude product was separated by chromatography on a silica gel column using hexane:diethyl ether (10:1) as the eluent. 4.2 g of 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyldecanal with a GC content of 90% was obtained. Mass spectrometry of the product m / z: 99(100), 43(23), 55(17), 81(13), 41(13), 69(11), 57(10), 98(8), 29(7), 100(7)

[0160] 3. Synthesis of the precursor 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanylhexanal (compound of formula (I) according to the present invention)

[0161] [Chemical formula]

[0162] Into a 500 mL stirring device 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 a nitrogen atmosphere. 12.7 g of (E)-hex-2-enal was added dropwise over 1 hour at 0 - 5 °C. Stirring was continued for 6 hours at 0 - 5 °C for the post-reaction. This mixture was washed twice with saturated sodium bicarbonate solution at room temperature, and then the solvent was evaporated using a rotary evaporator. 30.9 g of the crude product of 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyl-hexanal was obtained. For further purification, this crude product was separated by chromatography on a silica gel column using hexane:diethyl ether (10:1) as the eluent. 26.8 g of 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanylhexanal with a GC content of 90% was obtained. Mass spectrometry of the product m / z 99(100), 43(24), 55(15), 41(13), 81(12), 69(12), 100(6), 57(6), 170(6), 29(5), 98(5).

[0163] 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 (the compound of formula (I) according to the present invention)

[0164]

Chemical formula

[0165] Into 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. Stirring was continued at 0 - 5 °C for 6 hours for the post - reaction. This mixture was washed twice with saturated sodium bicarbonate solution at room temperature and then the solvent was evaporated using a rotary evaporator. 28.5 g of a crude product of 3 - [2 - methyl - 1 - (4 - methyltetrahydropyran - 2 - yl) propyl] sulfanyl - 1 - (2,6,6 - trimethyl - 1 - cyclohexen - 1 - yl) - 3 - butan - 2 - one was obtained. For further purification, this crude product was separated by chromatography on a silica gel column using hexane:diethyl ether (10:1) as the 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 with a GC content of 90% was obtained. Mass spectrometry of the product 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).

[0166] 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)

[0167]

Chemical formula

[0168] Into a 50 mL stirring device 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, 16.4 g of 8-ethoxytricyclo[5.2.1.02,6]decane-4-thiol and tetrahydrofuran (40 mL) were added at 0 °C under a 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 post-reaction. This mixture was washed twice with saturated sodium bicarbonate solution at room temperature and then the solvent was evaporated using a rotary evaporator. 30.4 g of the crude product of 8-ethoxytricyclo[5.2.1.02,6]decane-4-sulfanyl-1-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-1-one was obtained. Mass spectrometry of the product 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).

[0169] Synthesis procedure of the thiol according to the present invention

[0170] 1. 2-Methyl-1-[4-methyltetrahydropyran-2-yl]propane-1-thiol 2-Methyl-1-[4-methyltetrahydropyran-2-yl]propane-1-thiol was prepared according to International Publication No. WO 2019 / 037862 (A1).

[0171]

Chemical formula

[0172] 463 g of 4-methyl-2-(2-methyl-prop-1-enyl)tetrahydropyran and 228 g of thioacetic acid at 5-10 °C were added with 2.46 g of 2,2-azobis-(2-methyl-propionitrile, AIBN), and the mixture was stirred at room temperature for 30 minutes. Then, this mixture was slowly heated to 60 °C and stirred at 60 °C for 10 hours until complete conversion. After cooling to room temperature, 527.69 g (76%) of 2-methyl-(1-4-methyltetrahydropyran-2-yl)propyl-ethanethioate was obtained as a mixture of isomers by distillation (2.0 mbar, 104-110 °C). 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)。

[0173]

Chemical Structure

[0174] A solution of 501 g of 2-methyl-(1-4-methyltetrahydropyran-2-yl)propyl-ethanethioate in anhydrous methanol (3.3 L) was treated with 300 g of potassium carbonate and nitrogen and stirred overnight until complete conversion. Then, this mixture was acidified with 2 M hydrochloric acid (1 L), and 1 L 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 organic phases were combined, washed with brine (500 mL), dried over sodium sulfate, and concentrated in vacuo. This 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 a mixture of isomers. 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)。

[0175] 2. 8-Ethoxytricyclo[5.2.1.02,6]decane-4-thiol

[0176]

Chem.

[0177] To 583 g of 8-methoxytricyclo[5.2.1.02,6]dec-3-ene and 279 g of thioacetic acid at 5 - 10 °C, 2.91 g of 2,2-azobis-(2-methyl-propionitrile, AIBN) was added and stirred at room temperature for 30 minutes. Then, this mixture was 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) to give 773 g (91%) of (8-methoxytricyclo-4-[5.2.1.02,6]decan-1-yl)ethanethioate as a mixture of isomers.

[0178]

Chem.

[0179] A solution of 538 g of (8-methoxytricyclo-4-[5.2.1.02,6]decan-1-yl)ethanethioate in anhydrous methanol (3.3 L) was treated with 300 g of potassium carbonate and nitrogen and stirred overnight until complete conversion. The solvent was evaporated under reduced pressure, and 400 mL of MTBE was added. The organic phase was separated, and the aqueous phase was extracted with 200 mL of MTBE. The organic phases were combined, washed with saturated sodium bicarbonate solution, sodium sulfite solution and brine, dehydrated over sodium sulfate, and concentrated under reduced pressure. The crude product was purified by distillation (3.6 mbar, 99 - 102 °C) to give 376 g (90%) of 8-ethoxytricyclo[5.2.1.0 2,6 decane-4-thiol as a mixture of isomers. Mass spectrometry of the product 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).

[0180] Product according to the present invention

[0181] 1. Fabric softener

[0182]

Table 4

[0183] 2. Deodorant

[0184]

Table 5

[0185] 3. Shampoo

[0186]

Table 6

[0187] Sensory analysis

[0188] 1. Headspace gas chromatography / mass spectrometry

[0189] Application of the precursor in fabric softener (hand washing)

[0190] 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 Table 7 below for the composition of the softener) was added to 1 l of H2O in a 2 l beaker and mixed briefly to form a homogeneous solution.

[0191]

Table 7

[0192] Five pieces of cotton cloth (16×17 cm, 25 g each) were added and stirred for 30 minutes at room temperature using a magnetic stirrer. Then, these pieces of cotton cloth were individually wrung (about 60 g each) and dried with a certain ventilation at a temperature of 25 °C on a laundry rack in a self-made closed drying chamber (143 l). At a determined time point, volatile substances were adsorbed onto a Tenax® cartridge for 2 minutes at a continuous flow rate of 500 ml / min using a Gerstel gas sampling system.

[0193] One hour after the drying in this drying chamber, additional measurements were carried out in a self-made glass tube using two pieces of cloth. The two pieces of cloth were taken out from the laundry rack and placed into the glass tube (0.44 l) at room temperature. Using the Gerstel gas sampling system, volatile substances were adsorbed for 58 minutes first on a used Tenax cartridge® at a continuous air flow rate (500 ml / min), and then for 2 minutes on a new Tenax® cartridge. Next, sampling on the used Tenax® cartridge was continued until sampling on the new Tenax® cartridge was carried out for 2 minutes each at determined time points after 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 24 h, 48 h, 72 h. Then, these cartridges were desorbed at 260 °C on a Gerstel thermal desorption unit. The volatile substances were injected into an Agilent 6890 gas chromatograph equipped with a DB-1 MS column (30 m, 0.25 mm, 0.25 μm) connected to an Agilent mass spectrometer 5973N. The volatile substances were eluted at a flow rate of 1.4 ml / min of He using a temperature gradient that increased from 50 °C (for 4 minutes) to 260 °C at 8 °C / min.

[0194] The headspace concentration was calculated by external standard calibration using the corresponding fragrance materials at various concentrations (0.1, 0.25, 0.5, 1.0, 2.5, 5.0 ng / l) in EtOH. The corresponding fragrance materials are the fragrance materials released from the specific precursor / compound of formula (I), i.e., the corresponding α,β-unsaturated carbonyl compound and thiol compound. Desorption was carried out using the same conditions as described above, and each calibration solution (1 μl) was injected into a clean empty cartridge for analysis.

[0195] Figure 1. Fragrance release curve of the precursor 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]sulfanyldecanal (obtained according to procedure 2 described in the section on the synthesis procedure of the precursor above) determined by procedure 1 described above in the section on sensory analysis.

[0196] Figure 2. Fragrance release curve 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 procedure 1 described in the section on the synthesis procedure of the precursor above) determined by procedure 1 described above in the section on sensory analysis.

[0197] Figures 1 and 2 show the release of 2-methyl-1-(4-methyltetrahydropyran-2-yl)propanethiol and the respective α,β-unsaturated carbonyl compounds from the compound of formula (I) obtained according to procedures 1 and 2 described above in the section on the synthesis procedure of the precursor. The x-axis of these figures indicates the period during which the measurements were made. The y-axis shows the headspace concentrations of these two components released from the compound of formula (I) (determined according to procedure 1 described above in the section on sensory analysis), respectively. From these figures, it can be seen that a strong release of this thiol compound occurs in freshly laundered / wet laundry and is also sensorially recognizable. On the other hand, in dry laundry, a prominent release of the α,β-unsaturated carbonyl compound occurs with a time delay of several hours (2 - 48 hours for 2-decenal and 24 - 72 hours for δ-damascone) after a certain time. These analysis results demonstrate the (controlled) decomposition of the compound of formula (I) according to the present invention with the concomitant release of α,β-unsaturated aldehydes or ketones over time, which is consistent with the sensory evaluation of the laundry test (see below). The controlled decomposition of the compound of formula (I) advantageously results in a long-lasting perception of α,β-unsaturated aldehydes or ketones in dry laundry. Furthermore, this thiol compound with a strong influence improves the overall aroma of freshly laundered laundry without any undesirable off-notes, either unpleasant or otherwise.

[0198] For comparison, the experiment was repeated using a 1.0 g mixture of an α,β-unsaturated carbonyl compound (hexenal) and a thiol (2-methyl-1-(4-methyltetrahydropyran-2-yl)propane-1-thiol) instead of the compound of formula (I) according to the present invention.

[0199]

Table 8

[0200] The fragrance release from the compound of formula (I) according to the present invention is essentially different from that from a mixture of an α,β-unsaturated carbonyl compound and a thiol, and it can be seen that the released fragrance material is supplied from the partial decomposition of the compound of formula (I) according to the present invention over time. Surprisingly, it has been observed that the peak of thiol release is between 0 and 1 hour while the peak of hexenal release reaches at 4 to 7 hours, and surprisingly, the compound of formula (I) according to the present invention can supply two kinds of pleasant fragrance materials at different time points.

[0201] 2. Washing test

[0202] The sensory evaluation after the washing application of the compound of formula (I) according to the present invention (obtained according to Procedures 1 and 2 described above in the section of the synthetic procedure of the precursor) was carried out as described below, and the test results shown in Table 9 below were obtained. - Application of each compound of formula (I) according to the present invention in the perfume oil in a realistic use test - Perfume oil dosage 1% by weight in the softener (see Table 7 above for the composition of the softener) - Precursor dosage in the perfume oil is 2% by weight - Cotton woven fabric was washed in a washing machine at 30 °C using a short cycle program. - Sensory evaluation was carried out by 5 panelists. The intensity shown in Table 9 on a scale of 0 (no fragrance) to 9 (very strong fragrance) is the average of 3 evaluations by 3 panelists each. The fragrance descriptions shown in Table 9 are the average of 5 evaluations by 5 panelists each.

[0203]

Table 9

[0204] 3. Fabric softener

[0205] An appropriate amount of the compound of formula (I) was mixed with dipropylene glycol (DPG) in a perfume oil, and 1% of the resulting fragrance mixture was added to an unscented fabric softener to prepare a scented fabric softener sample.

[0206] 2 kg of cotton towels were washed in a European washing machine (Express 20 program, 20 °C, 800 rpm) using 30 g of the scented fabric softener (see Table 7 for the composition of this fabric softener). These fabrics were hung out to dry overnight and placed on a table for evaluation after 24 hours, 48 hours, and 72 hours. These fabrics were evaluated by 12 trained panelists. The perfume intensity was evaluated on a scale from no fragrance (0) to the strongest possible (10). The panelists were also asked to choose which sample was perceived to have a higher intensity.

[0207] It was concluded that fragrance recognition is significantly stronger when using the compound of formula (I) compared to an equivalent amount of δ-damascone. To emphasize this, a piece of cotton towel was analyzed by GC / MS according to Procedure 1 described above in the sensory analysis section, and the significantly increased headspace concentration of δ-damascone in the cotton towel washed with the perfume oil containing the compound of formula (I) was revealed.

[0208] [Table 10]

[0209] [Table 11]

[0210] [Table 12]

[0211] Fragrance release of the compound of formula (I), 3-[2-methyl-1-(4-methyltetrahydropyran-2-yl)propyl]-sulfanyl-1-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-1-one, and a mixture of 50% δ-damascone and 50% DPG

[0212]

Table 13

[0213] 4. Deodorant

[0214] An artificial skin model was prepared using synthetic skin (Vitro-Skin (registered trademark), about 2.5 cm radius), grease, cellulose, and agar.

[0215] A scented deo sample was prepared by mixing an appropriate amount of the compound of formula (I) with DPG in a perfume oil and adding 1% of the resulting fragrance mixture to an unscented deo substrate.

[0216] 100 mg of the scented deo is added to the artificial skin and evenly distributed for 15 seconds. Then, the model is placed on a heating plate (43 °C) and evaluated by 6 trained panelists after 0 h, 4 h, 24 h, and 48 h. The fragrance intensity is evaluated on a scale from no fragrance (0) to the strongest possible (9).

[0217] It is concluded that the fragrance intensity becomes significantly stronger when applying the perfume oil containing the compound of formula (I). Surprisingly, it is revealed that the recognition of the individual precursor components (thiol, α,β-unsaturated carbonyl) occurs not simultaneously but sequentially. The thiol component is recognized at 0 h, showing a richer fruity profile, while δ-damascone is recognized after 4 - 48 h and there is no recognition of the thiol note at all.

[0218]

Table 14

[0219] The panelists were asked to describe the difference in briskness between these different samples.

[0220] [Table 15]

[0221] [Table 16A] [Table 16B]

[0222] [Table 17]

[0223] 5. Shampoo

[0224] A scented shampoo sample was prepared by mixing an appropriate amount of the compound of formula (I) and DPG with perfume oil and adding 1% of the resulting fragrance mixture to an unscented shampoo base.

[0225] A set of slightly damp hair samples (2 g, white hair) was treated with 1 g of the scented shampoo and gently washed for 15 seconds. Then, the samples were left as they were for 30 seconds and rinsed with warm water (30 °C) for 15 seconds. Excess water was removed by passing the samples through the fingers.

[0226] The hair samples were hung to dry and evaluated by 5 trained panelists after 0 hours, 4 hours, and 24 hours. The fragrance intensity was evaluated on a scale from no fragrance (0) to the strongest possible (9).

[0227] [Table 18]

[0228] The panelists were asked to describe the difference in pleasantness between these different samples.

[0229]

Table 19

[0230]

Table 20

[0231]

Table 21

[0232] 6. Deodorant

[0233] An artificial skin model was prepared using synthetic skin (Vitro-Skin (registered trademark), approximately 2.5 cm radius), grease, cellulose, and agar.

[0234] An appropriate amount of the precursor was mixed with perfume oil, and a scented deodorant sample was prepared by adding 1% of the resulting fragrance mixture to an unscented deodorant substrate. 100 mg of the scented deodorant was added to the artificial skin and evenly distributed for 15 seconds. Then, the model was placed on a heating plate (43 °C) and evaluated by 12 trained panelists at 0 hours, 4 hours, 24 hours, and 48 hours. The fragrance intensity was evaluated on a scale from no fragrance (0) to the strongest possible (9).

[0235] The perfume oil containing the compound of formula (I) according to the present invention has been detected to be more strongly recognized in all stages of evaluation compared to the prior art perfume oil containing the precursor of International Publication No. 2015 / 032885 (A1), showing a distinct advantage of the compound of formula (I) according to the present invention. Surprisingly, both the fragrance speed profile and the recognized intensity after 0 hours are favorably affected by the introduction of the pleasant-smelling thiol component, while the excellent long-lasting performance at 6 to 24 hours is likely due to the lower evaporation profile / higher persistence of the compound of formula (I) according to the present invention.

[0236] [Table 22]

[0237] [Table 23]

[0238] [Table 24]

[0239] [Table 25]

[0240] [Table 26A] [Table 26B]

[0241] 7. Fabric softener

[0242] An appropriate amount of the compound of formula (I) and dipropylene glycol (DPG) were mixed with the perfume oil, and 1% of the resulting fragrance mixture was added to an unscented fabric softener to prepare a scented fabric softener sample.

[0243] A 2 kg cotton towel was washed in a European washing machine (Express 20 program, 20 °C, 800 rpm) using 30 g of a scented fabric softener (see Table 7 for the composition of this fabric softener). These fabrics were hung to dry overnight and placed on a table for evaluation after 0 hours, 24 hours, 48 hours, 72 hours, and 144 hours. These fabrics were evaluated by 15 trained panelists. The fragrance intensity was evaluated on a scale from no fragrance (0) to the strongest possible (10). The panelists were also asked to choose which sample was recognized at a higher intensity.

[0244] It was detected that the perfume oil containing the compound of formula (I) according to the present invention was more strongly recognized in all stages of evaluation compared to the prior art (perfume oil containing the precursor of International Publication No. 2015 / 032885 (A1)), showing a clear advantage of the compound of formula (I) according to the present invention. Surprisingly, both the fragrance pleasantness profile and the recognized intensity after 0 hours were favorably affected by the introduction of a pleasant-smelling thiol component, while the excellent long-lasting performance at 24 - 48 hours is likely due to the lower evaporation profile / higher persistence of the compound of formula (I) according to the present invention.

[0245] [Table 27]

[0246] [Table 28]

[0247] [Table 29]

Claims

1. Formula (I): 【Chemical 1】 A compound of (i) R is selected from the group consisting of hydrogen and C １ to C １０ linear or cyclic alkyl, alkenyl or alkadienyl residues, preferably said residues further having one, two or more C １ to C ４ linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents, R′ is selected from the group consisting of hydrogen and C １ to C １０ linear or cyclic alkyl, alkenyl or alkadienyl residues, preferably said residues further having one, two or more C １ to C ４ linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents, R １ is selected from the group consisting of hydrogen and C １ to C １０ linear or cyclic alkyl, alkenyl or alkadienyl residues, preferably said residues further having one, two or more C １ to C ４ linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents, R ２ is selected from the group consisting of C ４ to C １５ linear, cyclic or branched alkyl residues and further containing one, two or more functional groups selected from the group consisting of ether, alcohol and ketone, R ３ is selected from the group consisting of hydrogen and C １ to C １０ linear or cyclic alkyl, alkenyl or alkadienyl residues, preferably said residues further having one, two or more C １ to C ４ linear, cyclic or branched alkyl, alkenyl or alkadienyl substituents or Or, (ii) R′, R ２ and R ３ are each independently selected from the group defined in (i), and R and R １ are joined together to form a saturated or unsaturated ring system containing 5 to 10 carbon atoms, preferably, the ring system further has one, two or more C １ - C ５ linear, branched or cyclic alkyl, alkenyl or alkadienyl substituents, Or, (iii) R′, R １ and R ２ are each independently selected from the group defined in (i), R and R ３ are joined together to form a saturated or unsaturated, monocyclic or bicyclic ring system containing 5 to 10 carbon atoms and optionally containing one or two ether functional groups, preferably, the ring system further has one, two or more C １ - C ５ linear, branched or cyclic alkyl, alkenyl or alkadienyl substituents, Compound.

2. R is 【Chemical Formula 2】 The compound of formula (I) according to claim 1, selected from the group consisting of.

3. R′ is 【Chemical Formula 3】 The compound of formula (I) according to claim 1 or 2, selected from the group consisting of.

4. R １ is 【Chemical Formula 4】 The compound of formula (I) according to any one of claims 1 to 3, selected from the group consisting of.

5. R ２ is 【Chemical Formula 5A】 【Chemical Formula 5B】 A compound of formula (I) according to any one of claims 1 to 4, selected from the group consisting of

6. - The following: 【Chemical Formula 6A】 【Chemical Formula 6B】 【Chemical Formula 6C】 An α,β-unsaturated aldehyde or ketone selected from the group consisting of - The following: 【Chemical Formula 7A】 【Chemical Formula 7B】 【Chemical Formula 7C】 A thiol selected from the group consisting of A compound of formula (I) according to any one of claims 1 to 5, obtainable or obtainable by a [1,4]-addition reaction between

7. The compound of formula (I) is 【Chemical Formula 8A】 【Chemical Formula 8B】 【Chemical Formula 8C】 【Chemical Formula 8D】 【Chemical Formula 8E】 【Chemical Formula 8F】 【Chemical Formula 8G】 A compound of formula (I) according to any one of claims 1 to 6, selected from the group consisting of

8. The following components, (i) One or more compounds of formula (I) according to any one of claims 1 to 7, and (ii) One or more additional fragrance substances, A fragrance substance mixture containing or consisting of, preferably an essential oil.

9. The following A mixing step of one or more compounds of formula (I) according to any one of claims 1 to 7 and one or more additional fragrance substances; A method for producing a fragrance substance mixture according to claim 8, preferably a perfume, comprising or consisting of.

10. A perfumed product containing 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 a perfume, preferably in a sensually effective amount.

11. The perfumed product according to claim 10, wherein the product is a perfume extract, eau de parfum, eau de toilette, aftershave, eau de cologne, pre-shave product, splash cologne, perfumed refreshing cloth, acidic, alkaline and neutral detergents, fabric freshener, ironing aid, liquid detergent, powder detergent, laundry pretreatment agent, fabric softener, laundry soap, laundry tablet, bactericide, surface disinfectant, air freshener, aerosol spray, wax and polish, personal care product, hand cream and lotion, foot cream and lotion, depilatory cream and lotion, aftershave cream and lotion, shaving cream and lotion, hair care product, deodorant and antiperspirant, decorative cosmetic product, candle, kerosene, perfume stick, insecticide, insect repellent and fuel.

12. A method for producing a perfumed product, preferably the perfumed product according to claim 10 or 11, comprising the following (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 a perfume; (ii) providing one or more additional components of the perfumed product to be produced; (iii) contacting or mixing the additional component provided in step (ii) with the component provided in step (i) in a sensorially effective amount; A method comprising or consisting of.

13. Use of a compound of formula (I) according to any one of claims 1 to 7 as a precursor for the release of two or more different pleasant-smelling fragrance substances, preferably said two or more different fragrance substances are released and / or sensorially recognized at the same or different times, preferably different times.

14. A method for the release of two or more different pleasant-smelling fragrance substances, comprising the following: (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 perfumed product according to claim 10 or 11; (b) optionally applying or introducing the compound of formula (I) or the fragrance substance mixture or the perfumed product of step (a) to hair or skin or fabric fibers or to the surface to be perfumed or into the ambient air to be perfumed, preferably in a sensorially effective amount; (c) releasing two or more different pleasant-smelling fragrance substances from the compound of formula (I), preferably said two or more different pleasant-smelling fragrance substances are released and / or sensorially recognized at the same or different times, preferably different times; A method comprising or consisting of.

15. 【Chemical Formula 9A】 【Chemical Formula 9B】 A thiol selected from the group consisting of.

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