Compounds providing a persistent strawberry odor

Abstract

The present invention relates to a compound of formula (I) which is capable of producing octan-2- en-4-one and thus providing a persistent or tenacious strawberry odor to the environment. Moreover, the present invention relates to a method of imparting a persistent strawberry odor to a surface such as a hard surface, a fabric, skin or hair. Furthermore, the present invention relates to the use of said compound in the perfumery industry, as well as to a perfuming composition or a perfumed article comprising the compound of the present invention.

Description

Technical Field

[0001] This invention relates to the fragrance industry. More particularly, this invention relates to compounds of formula (I) capable of producing oct-2-en-4-one and thus providing a persistent or substantive strawberry scent to the environment. Furthermore, this invention relates to a method of imparting a persistent strawberry scent to surfaces such as hard surfaces, fabrics, skin, or hair. In addition, this invention relates to the use of said compounds in the fragrance industry, and to scented compositions or scented articles containing compounds of this invention. Background Technology

[0002] Consumers often associate the effectiveness of scented products with the perceived persistence or affinity of the fragrance. Fragrances (commodity fragrances) consist of a variety of volatile compounds that are applied to surfaces and evaporate from those surfaces to be smelled. Fragrances are applied to surfaces such as hard surfaces, fabrics, skin, or hair via fragrance compositions or scented consumer products such as fine air fresheners or various detergents and cleaning agents. Due to the high volatility of the aromatics that make up fragrances, the scent emanating from a scented surface can only be perceived for a limited time. In particular, the so-called top notes (top notes) of fragrances evaporate very quickly. They are the most volatile compounds in the composition and represent the freshness of the fragrance. Top notes typically include citrus, floral, green, and fruity notes, with fruity notes being particularly appreciated by consumers. Several classes of fruity notes are used in fragrances, such as red berry notes like raspberry or strawberry. Oct-2-en-4-one can be used as a fragrance ingredient when used in fragrance compositions or scented consumer products to provide a natural strawberry scent. However, the compound is quite volatile, and the odor it imparts to surfaces (such as hard surfaces, fabrics, skin, or hair) lasts only a relatively short time.

[0003] Consumers seek fragrances that are stable and long-lasting or pleasantly detectable for hours or even days after application, particularly long-lasting red berry scents such as strawberry.

[0004] Therefore, an object of the present invention is to provide a system capable of conveying a lasting or pleasant strawberry scent to the environment. Furthermore, another object of the present invention is to find a method for imparting a lasting strawberry scent to surfaces such as hard surfaces, fabrics, skin, or hair by applying a fragrance composition or a fragranced product. Summary of the Invention

[0005] We have now discovered that certain compounds derived from oct-2-en-4-one can be advantageously used to impart a persistent or affinity for strawberry scents from a given surface to the environment, and thus can be used as ingredients in flavored compositions or flavored products.

[0006] Therefore, the first object of the present invention relates to compounds of formula (I),

[0007]

[0008] in

[0009] n represents an integer from 1 to 6;

[0010] A represents C2 to C with n valences. 22 The hydrocarbon group optionally comprises one to eight ether groups and / or one or two functional groups selected from the group consisting of alcohols, ketones, aldehydes, esters, thioethers, carboxylic acids, alkali metal carboxylates, amines, amides, carbamates, nitriles, or thiols; and

[0011] X represents a group from formulas (i) to (vi).

[0012]

[0013] In the formula, the wavy line indicates the position of the bond between carbon 2 and X, the shaded line indicates the position of the bond between X and A, and R independently represents a hydrogen atom or a straight-chain or branched hydrocarbon group from C1 to C4, provided that the shaded line is not directly connected to a heteroatom or carbonyl functional group of A, and that 2-(propylthio)oct-4-one, 4-(benzyloxy)benzoic acid 4-oxooct-2-yl ester, 2-(methoxymethoxy)oct-4-one, 2-((2-methoxyethoxy)methoxy)oct-4-one, 2-(ethylamino)oct-4-one and 2-(benzylamino)oct-4-one.

[0014] If n > 1, then each X independently represents any one of the groups in formulas (i) to (vi). Preferably, if n > 1, then each X represents the same group selected in formulas (i) to (vi).

[0015] It should be understood that the use of "...alkyl group..." indicates that the group consists of hydrogen and carbon atoms and can be in the form of an aliphatic hydrocarbon, i.e., a straight-chain or branched saturated hydrocarbon (e.g., alkyl), a straight-chain or branched unsaturated hydrocarbon (e.g., alkenyl or ynyl), a saturated cyclic hydrocarbon (e.g., cycloalkyl), or an unsaturated cyclic hydrocarbon (e.g., cycloalkenyl or cycloynyl), or in the form of an aromatic hydrocarbon, i.e., an aryl group, or in the form of a mixture of groups of the aforementioned types. For example, unless specifically limited to only one type mentioned, a particular group may contain a straight-chain alkyl, a branched alkenyl (e.g., having one or more carbon-carbon double bonds), a (poly)cycloalkyl, and an aryl moiety. Similarly, in all embodiments of the invention, when a group is mentioned in more than one type of topological (e.g., straight-chain, cyclic, or branched) and / or saturated or unsaturated (e.g., alkyl, aromatic, or alkenyl) form, it also means that it may contain a group having any of the aforementioned topologies or saturated or unsaturated moieties as described above. Similarly, in all embodiments of the invention, when a group is referred to as being in a saturated or unsaturated form (e.g., alkyl), it means that the group can be any type of topology (e.g., straight-chain, cyclic, or branched) or have several parts with various topological structures.

[0016] It should be understood that the terms "...hydrocarbon group, optionally containing..." or "...hydrocarbon group, optionally substituted with..." mean that the hydrocarbon group optionally contains an alcohol, ketone, aldehyde, ether, thioether, ester, carboxylic acid, alkali metal carboxylate, amine, amide, carbamate, nitrile, or thiol group. These groups may substitute the hydrogen atom of the hydrocarbon group and thus side-attach to the hydrocarbon, or substitute the carbon atom of the hydrocarbon group (if chemically possible) and thus insert into the hydrocarbon chain. For example, -CH2-CH2-CHOH-CH2- group represents a C4 hydrocarbon group containing an alcohol group (substitution of hydrogen atom), -CH2-CH2-COO-CH2-CH2-OCO-CH2-CH2- group represents a C8 hydrocarbon group containing two ester groups (substitution of carbon atoms / insertion into the hydrocarbon chain), and similarly, -CH2-CH2-O-CH2-CH2-O-CH2-CH2- represents a C6 hydrocarbon group containing two ether groups. In contrast, the expression "...alkyl or alkenyl, optionally substituted with..." refers to an alkyl or alkenyl group in which at least one hydrogen atom can be substituted by a functional group.

[0017] According to any embodiment of the invention, X preferably represents a group of formula (i) to (iv) or (vi), more preferably a group of formula (i) to (iii) or (vi), even more preferably a group of formula (i) to (iii), and most preferably a group of formula (i).

[0018] According to any embodiment of the invention, n is preferably an integer varying between 1 and 4, more preferably between 1 and 2, and even more preferably, n can be 1.

[0019] According to any embodiment of the invention, A can represent n-valent C2 to C 22 The hydrocarbon group optionally comprises one to eight ether groups and / or one or two functional groups selected from the group consisting of alcohols, ketones, aldehydes, esters, thioethers, carboxylic acids, alkali metal carboxylates, amines, amides, carbamates, nitriles, or thiols. Preferably, A may represent an n-valent C2 to C3 group. 18 The hydrocarbon group optionally comprises one to four ether groups and / or one or two functional groups selected from the group consisting of alcohols, ketones, aldehydes, esters, carboxylic acids, amines, amides, or carbamates. Preferably, A may represent a monovalent or divalent C2 to C3 group. 18 The hydrocarbon group optionally comprises one to four ether groups and / or one or two functional groups selected from the group consisting of alcohols, ketones, esters, carboxylic acids, amines, amides, or carbamates. Preferably, A may represent a benzyl group or a monovalent or divalent C2-C group. 18 Alkyl or alkenyl groups, optionally substituted with one to four C atoms. 1-4 Ether groups and / or one or two groups derived from alcohols, ketones, C 1-10 Esters, carboxylic acids, amines, C 1-4 amide or C 1-4 Functional groups selected from the group consisting of carbamates. Preferably, A may represent benzyl or monovalent or divalent C2-C. 18 Alkyl or alkenyl groups, which may optionally be substituted with one or two of the groups derived from alcohols, ketones, C 1-4 Esters, carboxylic acids, amines, or C 1-4 Functional groups selected from the group consisting of carbamates. Preferably, A may represent benzyl or a monovalent C4 to C5 group. 16 Alkyl or alkenyl or monovalent C2 to C4 alkyl, optionally substituted with one or two of the derivatives of alcohols, ketones, C4 alkyl groups. 1-4 Esters, carboxylic acids, amines, or C 1-4 The functional group selected from the group consisting of carbamates, or A may represent a divalent C2 to C6 alkyl group, which may optionally be substituted with one or two of the functional groups derived from alcohols, ketones, C 1-4 Esters, carboxylic acids, amines, or C 1-4 Functional groups selected from the group consisting of urethane esters. Preferably, A may represent a benzyl group or a monovalent C5 to C15 alkyl or alkenyl group. Preferably, A may represent a monovalent C6 to C15 alkyl group. 14 Alkyl or alkenyl. Even more preferably, A can represent a monovalent C6 to C6 group. 14 Straight-chain alkyl or alkenyl groups.

[0020] According to any of the above embodiments, the compound of formula (I) is 2-(alkylthio)oct-4-one, wherein the alkyl group is C6 to C4. 18 Between C6 and C 14Variations between these, such as 2-(octylthio)oct-4-one or 2-(dodecylthio)oct-4-one; 2- or 3-((4-oxooct-2-yl)thio)propionic acid derivatives, such as 2-((4-oxooct-2-yl)thio)propionic acid, 3-((4-oxooct-2-yl)thio)propionic acid or 2-methyl-3-((4-oxooct-2-yl)thio)propionic acid; 2-((hydroxyalkyl)thio)oct-4-one derivatives, wherein the alkyl group is C2 to C3. 18 Between C2 and C 10 Variations between these ranges, for example, 2-((2-hydroxyethyl)thio)oct-4-one; (2-((4-oxooct-2-yl)thio)alkyl)carbamate alkyl ester derivatives, wherein the alkyl group is C2 to C3. 18 The size of the alkyl group varies between C2 and C6, for example, tert-butyl (2-((4-oxooct-2-yl)thio)ethyl)carbamate; 2-(alkylamino)oct-4-one, wherein the size of the alkyl group is between C6 and C7. 18 Between C6 and C 14 Variations between these, such as 2-(dodecylamino)oct-4-one; 2-((4-oxooct-2-yl)amino)carboxylic acid, derived from natural or non-natural amino acids, such as glycine, alanine, phenylalanine, arginine, histidine, lysine, aspartic acid, glutamic acid, cysteine, methionine, glutamine, asparagine, threonine, serine, leucine, isoleucine, valine, tyrosine, or tryptophan; 2-((4-oxooct-2-yl)amino)carboxylic acid alkyl Esters, derived from the aforementioned natural or non-natural amino acids, wherein the size of the alkyl group varies between C1 and C4; N,S-bis(4-oxooct-2-yl)-L-cysteine; N,S-bis(4-oxooct-2-yl)cysteine ​​alkyl esters, wherein the size of the alkyl group varies between C1 and C4, such as N,S-bis(4-oxooct-2-yl)-L-cysteine ​​methyl ester; 2-(alkylsulfinyl)oct-4-one, wherein the size of the alkyl group varies between C6 and C4. 18 Between C6 and C 14 Variations exist between these, for example, 2-(dodecylsulfinyl)oct-4-one; 2-(alkylsulfonyl)oct-4-one, wherein the alkyl group is C6 to C4. 18 The variation between C6 and C is best observed between C6 and C6. 14 Variations between, for example, 2-(dodecylsulfonyl)oct-4-one; 4-oxooct-2-yl esters of alkyl or olefinic acids, wherein the size of the alkyl or alkenyl group is between C6 and C7. 18 Between C6 and C 14Variations between these, for example, undecano-10-enoic acid 4-oxooct-2-yl ester; or mono- or poly(4-oxooct-2-yl)aryl carboxylic acid esters, wherein the aryl carboxylic acid ester group is benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, or trimellitic acid. Preferably, the compound of formula (I) is 2-(alkylthio)oct-4-one, 2-(alkylsulfinyl)oct-4-one, 2-(alkylsulfonyl)oct-4-one, or a 4-oxooct-2-yl ester of an alkyl acid or an olefinic acid, wherein the size of each alkyl or alkenyl group is from C6 to C6. 18 Between C6 and C 14 Variations between these, such as 2-(octylthio)oct-4-one, 2-(dodecylthio)oct-4-one, 2-(dodecylsulfinyl)oct-4-one, 2-(dodecylsulfonyl)oct-4-one, or undecano-10-enoic acid 4-oxooct-2-yl ester.

[0021] Over time, the compounds according to formula (I) can slowly produce oct-2-en-4-one, thus contributing a persistent strawberry aroma to the environment. These compounds are themselves non-volatile and essentially odorless. They are also relatively stable in flavored compositions or already flavored products. When exposed to surfaces under environmental conditions, oct-2-en-4-one can be considered to form through a reaction with ambient moisture. The presence of oxygen in the air, changes in pH, the presence of enzymes, or increases in temperature, as well as other types of mechanisms or combinations thereof, can further trigger the formation of oct-2-en-4-one.

[0022] The non-volatile and essentially odorless compound is characterized by a vapor pressure below 2.0 Pa, calculated using software EPIwin v.3.10 (2000, available from the U.S. Environmental Protection Agency). Preferably, the vapor pressure is below 0.2 Pa, or even more preferably below 0.02 Pa.

[0023] Oct-2-en-4-one can be produced from compounds of formula (I) in (E) form, (Z) form, or a mixture thereof. Preferably, (E)-oct-2-en-4-one or a mixture of (E / Z)-oct-2-en-4-one with the (E)-isomer as the main component is produced.

[0024] Compounds of formula (I) can be synthesized from oct-2-en-4-one using conventional methods. Preferably, they are synthesized from (E)-oct-2-en-4-one or a mixture of (E / Z)-oct-2-en-4-one with the (E)-isomer as the main component. Generally, the compounds of the present invention can be synthesized from oct-2-en-4-one with formula [HX-]. n The [1,4]-addition reaction between compounds of -A is given, where all symbols have the meaning shown in formula (I).

[0025] Although it is not possible to provide a formula [HX-] that can be used to synthesize the compounds of this invention. n A detailed list of -A compounds is provided, but the following may be listed as preferred and non-limiting examples: hexane-1-thiol, octane-1-thiol, dodecane-1-thiol, hexadecane-1-thiol, octadecane-1-thiol, 2-mercaptoacetic acid, methyl or ethyl 2-mercaptoacetic acid, 2-mercaptopropionic acid, methyl or ethyl 2-mercaptopropionate, 3-mercaptopropionic acid, methyl or ethyl 3-mercaptopropionate, 3-mercapto-2-methylpropionic acid, methyl or ethyl 3-mercapto-2-methylpropionate, 2-mercaptoethanol, (2 1-Mercaptoethyl) tert-butyl carbamate, 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine, methyl or ethyl 2-amino-3-mercaptopropionate or their corresponding hydrochlorides, natural or non-natural amino acids such as glycine, alanine, phenylalanine, arginine, histidine, lysine, aspartic acid, glutamic acid, cysteine, methionine, glutamine, asparagine, threonine, serine, leucine, isoleucine, valine, tyrosine or tryptophan, and their corresponding methyl or ethyl esters.

[0026] Compounds of formula (I) can also be obtained by conventional methods via esterification of 2-hydroxyoct-4-one. Preferably, they are derived from 2-hydroxyoct-4-one and [ClCOCR2]. n Synthesis of -A acyl chlorides, where all symbols have the meaning shown in formula (I).

[0027] Although it is not possible to provide a formula [ClCOCR2] that can be used to synthesize the compounds of this invention. n A comprehensive list of -A acyl chlorides is available, but saturated, unsaturated, or aromatic C6 to C6 chlorides can be listed. 18 Acyl chlorides of carboxylic acids are preferred and non-limiting examples, such as: octanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octenic acid, decenoic acid, decadienoic acid, undecenoic acid, myrcenoic acid, laurolinoleic acid, 4-hexadecenoic acid, oleic acid, linoleic acid, adipic acid, pimelic acid, sebacic acid, dodecanoic acid, propionic acid-1,2,3-triic acid, aconitic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, or pyromellitic acid.

[0028] According to any embodiment, the compound of formula (I) is encapsulated. At least one compound of formula (I) can be encapsulated in microcapsules. In one embodiment, at least one compound of formula (I) is encapsulated in a core-shell microcapsule, wherein the compound of formula (I) is contained within a core surrounded by a shell. The shell of the microcapsule protects the compound of formula (I) from environmental influences. The shell is made of a material capable of releasing the compound of formula (I). In one embodiment, the shell is made of a material capable of releasing the compound of formula (I) upon shell rupture and / or by diffusion through the shell. Methods for preparing said microcapsules are well known to those skilled in the art.

[0029] The properties of the polymer shell from the microcapsules of this invention can vary. As a non-limiting example, the shell can be amino-plastic based, polyurea-based, or polyurethane-based. The shell can also be composite, i.e., organic-inorganic, such as a composite shell composed of at least two cross-linked inorganic particles, or a shell produced by the hydrolysis and condensation reaction of a polyalkoxysilane macromonomer composition.

[0030] According to one embodiment, the shell comprises an amino plastic copolymer, such as melamine-formaldehyde or urea-formaldehyde or cross-linked melamine-formaldehyde or melamine-glyoxal.

[0031] According to another embodiment, the shell is polyurea-based, made from, for example but not limited to, isocyanate-based monomers and amine-containing crosslinking agents such as guanidine carbonate and / or guanidineazole. Preferred polyurea-based microcapsules comprise: a polyurea wall, which is a polymerization product of at least one polyisocyanate containing at least two isocyanate functional groups and at least one amine selected from amines (e.g., water-soluble guanidine salts and guanidine); a colloidal stabilizer or emulsifier; and an encapsulating fragrance. However, the use of amines may be omitted.

[0032] According to one particular embodiment, the colloidal stabilizer comprises an aqueous solution of 0.1% to 0.4% polyvinyl alcohol, 0.6% to 1% vinylpyrrolidone, and a cationic copolymer of quaternized vinylimidazolium (all percentages are defined by weight relative to the total weight of the colloidal stabilizer). According to another embodiment, the emulsifier is an anionic or amphiphilic biopolymer, preferably selected from gum arabic, soy protein, gelatin, sodium caseinate, and mixtures thereof.

[0033] According to another embodiment, the shell is polyurethane-based and made of, for example but not limited to, polyisocyanates and polyols, polyamides, polyesters, etc.

[0034] The preparation of aqueous dispersions / slurries of core-shell microcapsules is well known to those skilled in the art. On one hand, the microcapsule wall material may comprise any suitable resin, and particularly includes melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, etc. Suitable resins include reaction products of aldehydes and amines, with suitable aldehydes including formaldehyde and glyoxal. Suitable amines include melamine, urea, benzoguanidine, glycyrrhizin, and mixtures thereof. Suitable melamines include hydroxymethyl melamine, methylated hydroxymethyl melamine, iminomelamine, and mixtures thereof. Suitable ureas include dihydroxymethyl urea, methylated dihydroxymethyl urea, urea-resorcinol, and mixtures thereof. Suitable manufacturing materials may be obtained from one or more of Solutia Inc. (St. Louis, Missouri USA), Cytec Industries (West Paterson, New Jersey USA), and Sigma-Aldrich (St. Louis, Missouri USA).

[0035] According to a specific implementation, the core-shell microcapsules are formaldehyde-free capsules. A typical method for preparing formaldehyde-free microcapsule slurries that do not contain amino plastics includes the following steps: 1) preparing an oligomeric composition comprising a reaction product containing, or an oligomeric composition obtained by reacting the following components together:

[0036] a) A polyamine component in the form of melamine or a mixture of melamine and at least one C1-C4 compound containing two NH2 functional groups;

[0037] b) Glyoxal, C 4-6 An aldehyde component in the form of a mixture of 2,2-dialkoxyacetaldehyde and optionally glyoxylate, wherein the glyoxal / C ratio of the mixture is... 4-6 The molar ratio of 2,2-dialkoxyethanol is from 1 / 1 to 10 / 1; and

[0038] c) Protic acid catalysts;

[0039] 2) Prepare an oil-in-water dispersion, wherein the droplet size is 1–600 μm, and comprises:

[0040] i.Oil;

[0041] ii. Water medium

[0042] iii. At least one oligomer composition as obtained in step 1;

[0043] iv. At least one crosslinking agent selected from the following:

[0044] A)C4-C 12Aromatic or aliphatic di or triisocyanates and their biuret, triuret, trimers, trimethylolpropane adducts and mixtures thereof; and / or

[0045] B) Di- or tri-epoxyethylene compounds of the following formula

[0046] A-(ethylene oxide-2-ylmethyl) n

[0047] Where n represents 2 or 3, and l represents a C2-C6 group that may contain 2 to 6 nitrogen and / or oxygen atoms;

[0048] v. Optionally, a C1-C4 compound containing two NH2 functional groups;

[0049] 3) Heat the dispersion;

[0050] 4) Cool the dispersion.

[0051] The method is described in more detail in WO2013 / 068255, the contents of which are included here by reference.

[0052] According to another embodiment, the shell of the microcapsule is polyurea-based or polyurethane-based. Examples of methods for preparing polyurea-based and polyurethane-based microcapsule slurries are described, for example, in WO2007 / 004166, EP2300146, and EP2579976, the contents of which are also incorporated herein by reference. Methods typically used to prepare polyurea-based or polyurethane-based microcapsule slurries include the following steps:

[0053] a) Dissolving at least one polyisocyanate having at least two isocyanate groups in oil to form an oil phase;

[0054] b) Prepare an aqueous solution of the emulsifier or colloidal stabilizer to form an aqueous phase;

[0055] c) The oil phase is added to the aqueous phase to form an oil-in-water dispersion, wherein the average droplet size is 1 to 500 μm, preferably 5 to 50 μm;

[0056] d) Apply conditions sufficient to initiate interfacial polymerization and form microcapsules in slurry form.

[0057] Examples of microcapsules suitable for use in this invention include, but are not limited to, the microcapsules disclosed in International Patent Application Publication No. WO 2007 / 026307 A2. Other examples include the microcapsules disclosed in International Patent Application Publication No. WO 2014 / 029695 A1. Further examples include the microcapsules disclosed in International Patent Application Publication No. WO 2006 / 006003 A1. Further examples include the microcapsules disclosed in International Patent Application Publication No. WO 2006 / 018964 A1. Further examples include the microcapsules disclosed in International Patent Application Publication No. WO 2007 / 096790 A1. Further examples include the microcapsules disclosed in International Patent Application Publication No. WO 2009 / 153695 A1. Further examples include the microcapsules disclosed in European Patent No. EP2379047.

[0058] Examples of methods for encapsulating (I) compounds include, but are not limited to, the microcapsules disclosed in International Patent Application Publication No. WO 2007 / 026307 A2. Other examples include the microcapsules disclosed in International Patent Application Publication No. WO 2014 / 029695 A1. Further examples include the microcapsules disclosed in International Patent Application Publication No. WO 2006 / 006003 A1. Further examples include the microcapsules disclosed in International Patent Application Publication No. WO 2006 / 018964 A1. Further examples include the microcapsules disclosed in International Patent Application Publication No. WO 2007 / 096790 A1. Further examples include the microcapsules disclosed in International Patent Application Publication No. WO 2009 / 153695 A1. Further examples include the microcapsules disclosed in European Patent No. EP2379047.

[0059] As described above, the present invention relates to the use of compounds of formula (I) as flavoring ingredients in providing a lasting strawberry scent to the environment. In other words, it relates to a method or process for imparting, enhancing, improving, or altering the strawberry scent characteristics of a flavored composition, flavored article, or surface, the method comprising adding an effective amount of at least one compound of formula (I) to said composition or article. By "use of compounds of formula (I)," it must also be understood herein to be the use of any composition containing a compound of formula (I) and which can be advantageously used in the fragrance industry.

[0060] As a "fragrant ingredient," it refers to a compound used in a fragrance preparation or composition to impart a pleasurable effect. In other words, for a fragrance ingredient to be considered a fragrance ingredient, it must be recognized by those skilled in the art as capable of imparting or altering the odor of a composition in an active or pleasant manner, rather than merely having an odor.

[0061] The description of "strawberry aroma" or "strawberry scent" should be understood as an aroma reminiscent of strawberry fruit. For example, compounds described as having a strawberry aroma include oct-2-en-4-one and 2,5-dimethyl-4-hydroxy-2H-furan-3-one. 5-Ethyl-4-hydroxy-2-methyl-3(2H)-furanone, 2,5-dimethyl-4-oxo-4,5-dihydrofuran-3-yl ester, ethyl 3-methyl-3-phenylethylene oxide-2-carboxylate (Strawberry) ), ethyl 3-phenylethylene oxide-2-carboxylate, methyl 2-acetaminobenzoate or 3-phenylpropyl 3-methylbutyrate, 2-methyl-4-oxo-4H-pyran-3-yl propionate, 2-methylpent-2-enoic acid or (2S,5S)-2-(tert-butyl)-5-methyl-2-propyltetrahydrofuran

[0062] For clarity, a persistent effect is generally achieved if, after a certain period of time, such as hours or days, a given compound releases a stronger odor into the environment than a reference compound that provides the same type of odor. Therefore, when referring to compounds of formula (I) of the present invention, the expression “persistent strawberry odor” should be understood as an increase in the duration of the perceived strawberry odor (release of oct-2-en-4-one into the atmosphere) compared to the perception of a single oct-2-en-4-one molecule, measured under the same conditions (e.g., after hours (6 or 8 hours) or days (1 or 3 days)).

[0063] In fact, the composition described herein is also an object of the present invention as an advantageous flavoring ingredient.

[0064] Therefore, another object of the present invention is a flavoring or aromatizing composition comprising:

[0065] i) at least one compound of the present invention as defined above, used as a flavoring or aromatizing ingredient;

[0066] ii) at least one ingredient selected from the group consisting of a seasoning or spice carrier and a seasoning or spice base; and

[0067] iii) Optionally, at least one seasoning or spice condiment.

[0068] Preferably, the composition of the present invention is a flavoring composition.

[0069] The term "fragrance carrier" refers to a material that is neutral from the perspective of fragrance, meaning it does not significantly alter the sensory properties of the flavoring ingredients. The carrier can be liquid or solid.

[0070] As liquid carriers, emulsion systems, i.e., solvent and surfactant systems, or solvents commonly used in fragrances, can be listed as non-limiting examples. A detailed description of the properties and types of solvents commonly used in fragrances is impossible to exhaust. However, solvents such as butanediol or propylene glycol, glycerol, dipropylene glycol and its monoethers, 1,2,3-propanetriyltriacetate, dimethyl glutarate, dimethyl adipate, 1,3-diacetoxypropyl-2-yl acetate, diethyl phthalate, isopropyl myristate, benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethanol, triethyl citrate, or mixtures thereof are the most commonly used. For compositions containing both fragrance carriers and fragrance bases, in addition to those detailed above, other suitable fragrance carriers may also be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins, such as those marketed under trademarks. Those known to the public (source: Exxon Chemical), or glycol ethers and glycol ether esters, such as those marketed under trademarks Those commonly known (source: Dow Chemical Company), or hydrogenated castor oil, such as those marketed as trademarks... RH 40, those that are well-known (Source: BASF).

[0071] A solid carrier is a material to which a flavoring composition or certain components of a flavoring composition can be chemically or physically bonded. Such solid carriers are typically used to stabilize compositions or to control the evaporation rate of compositions or certain components. Solid carriers are currently used in the art, and those skilled in the art know how to achieve the desired effects. However, as non-limiting examples of solid carriers, examples include absorbent resins or polymers or inorganic materials such as porous polymers, cyclodextrins, wood-based materials, organic or inorganic gels, clay, gypsum, talc, or zeolite.

[0072] Other non-limiting examples of solid carriers include encapsulating materials. Examples of such materials may include wall-forming and plasticizing materials, such as monosaccharides, disaccharides, or trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, proteins, or pectins, or as described in references such as H. Scherz, Hydrokolloide: Stabilisatoren, Dickungs- und Geliermittel in Lebensmitteln, Band 2der Schriftenreihe Lebensmittelchemie, The materials listed in Behr's Verlag GmbH & Co., Hamburg, 1996. Encapsulation is a method well known to those skilled in the art and can be carried out, for example, by using techniques such as spray drying, agglomeration, or extrusion; or by encapsulation of coatings including agglomeration and composite agglomeration techniques.

[0073] As a non-limiting example of a solid carrier, a core-shell capsule may be specifically cited, which uses resins of the type of amino plastics, polyamides, polyesters, polyureas, or polyurethanes, or mixtures thereof (all of which are well known to those skilled in the art), and is carried out by a phase separation method initiated by using techniques such as polymerization, interfacial polymerization, coagulation, or these techniques together (all of which have been described in the prior art), and optionally in the presence of a polymer stabilizer or a cationic copolymer.

[0074] Resins can be produced by polycondensation of aldehydes (e.g., formaldehyde, 2,2-dimethoxyacetaldehyde, glyoxal, glyoxylic acid, or hydroxyacetaldehyde and mixtures thereof) with amines such as urea, benzoguanamine, glycoluryl, melamine, hydroxymethyl melamine, methylated hydroxymethyl melamine, guanidine, etc., and mixtures thereof. Alternatively, pre-formed resins can be used to alkylate polyamines, for example, under trademarks. (Source: Cytec Technology Corp.), Cy (Source: Cytec Technology Corp.) or (Source: BASF) Those that are commercially available.

[0075] Other resins are produced by the formation of trimers from polyols such as glycerol and polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, or phenyl diisocyanate, or biuret of hexamethylene diisocyanate, or trimers of phenyl diisocyanate and trimethylolpropane (as trade name). Known, those produced by the condensation polymerization of (source: Mitsui Chemicals) in which phenyl diisocyanate is a trimer of trimethylolpropane and hexamethylene diisocyanate is a biuret.

[0076] Some research literature relating to the encapsulation of fragrances via the condensation of melamine resins with aldehydes includes articles such as those by K. Dietrich et al., Acta Polymerica, 1989, vol. 40, pages 243, 325, and 683, and 1990, vol. 41, page 91. These articles have described various parameters affecting the preparation of such core-shell microcapsules according to prior art methods, which are further detailed and exemplified in patent literature. Wiggins Teape Group Limited's US 4'396'670 is a relevant early example of the latter. Since then, many other authors have enriched the literature in this field, and it is impossible to cover all published advances here, but general knowledge of encapsulation techniques is essential. More recent targeted publications also address suitable uses of such microcapsules, such as the article by HY Lee et al., Journal of Microencapsulation, 2002, vol. 19, pages 559-569, and International Patent Publication WO01 / 41915 or S. The article by Chimia et al., 2011, vol. 65, pages 177-181, is representative.

[0077] The term "fragrance base" refers to a composition containing at least one flavoring ingredient.

[0078] The flavoring agent is not of formula (I). Furthermore, by "flavoring agent," it refers here to a compound used in a flavoring preparation or composition other than the flavoring agent of formula (I), and imparts, for example, a pleasurable effect to the flavoring agent of formula (I). In other words, for such an agent to be considered a flavoring agent, it must be recognized by those skilled in the art as capable of imparting or altering the odor of a composition in an active or pleasant manner, and not merely possessing an odor.

[0079] In particular, flavoring agents that can be used in flavoring formulations or compositions according to the present invention include, as non-limiting examples:

[0080] a) Natural or similar ingredients and natural extracts, preferably those obtained from red berries (e.g., strawberries or raspberries);

[0081] b) Ingredients with strawberry scent, such as oct-2-en-4-one and 2,5-dimethyl-4-hydroxy-2H-furan-3-one. 5-Ethyl-4-hydroxy-2-methyl-3(2H)-furanone, 2,5-dimethyl-4-oxo-4,5-dihydrofuran-3-yl ester, ethyl 3-methyl-3-phenylethylene oxide-2-carboxylate (Strawberry) ), ethyl 3-phenylethylene oxide-2-carboxylate, methyl 2-acetaminobenzoate or 3-phenylpropyl 3-methylbutyrate, 2-methyl-4-oxo-4H-pyran-3-yl propionate, 2-methylpent-2-enoic acid or (2S,5S)-2-(tert-butyl)-5-methyl-2-propyltetrahydrofuran

[0082] c) Ingredients with raspberry aroma, such as 4-(4-methoxyphenyl)but-2-one (raspberry ketone);

[0083] d) Ingredients with other fruity aromas, such as ethyl butyrate, 5-heptyldihydrofuran-2(3H)-one, and ethyl 2-(2-methyl-1,3-dioxolane-2-yl)ethyl acetate. Or diethyl cyclohexane-1,4-dicarboxylate

[0084] e) Ingredients with caramel notes, such as 2-ethyl-3-hydroxy-4H-pyran-4-one;

[0085] f) Ingredients with citrus notes, such as 1-methyl-4-(1-methylvinyl)-cyclohexene (limonene);

[0086] g) Ingredients with floral and citrus notes, such as methyl 2-(3-oxo-2-pentylcyclopentyl)acetate.

[0087] h) Ingredients with floral notes, such as 3,7-dimethyloctyl-1,6-dien-3-ol (linalool), 3-methylbutyl 2-hydroxybenzoate, hexyl 2-hydroxybenzoate, benzyl 2-hydroxybenzoate, or cyclohexyl 2-hydroxybenzoate.

[0088] i) Ingredients with floral and woody notes, such as (E)-4-(2,6,6-trimethylcyclohexyl-1- or 2-en-1-yl)but-3-en-2-one (β- or α-ionone), (E)-4-(2,2-dimethyl-6-methylenecyclohexyl)but-3-en-2-one (γ-ionone), or 1-(octahydro-2,3,8,8-tetramethyl-2-naphthyl)-1-ethylone (Iso E) (mixture of isomers);

[0089] j) Components with a green aroma, such as (Z)-hex-3-en-1-ol, (Z)-hex-3-en-1-yl acetate, (Z)-hex-3-en-1-yl butyrate, (Z)-hex-3-en-1-yl benzoate, (Z)-hex-3-en-1-yl 2-hydroxybenzoate, and 1-(3,3- or 5,5-dimethylcyclohex-1-en-1-yl)pent-4-en-1-one.

[0090] k) Components with a musky aroma, such as oxane-2-one Oxyhexadecane-12- and / or 13-en-2-enone 3-Methylcyclopentadecano-1-one (Z)-3-Methylcyclopentadecan-5-en-1-one Or 2-(1-(3,3-dimethylcyclohexyl)ethoxy)-2-methylpropyl propionate

[0091] Furthermore, those skilled in the art can select other fragrance additives based on common sense and according to the intended use or application and the desired sensory effect. The nature and type of these other fragrance additives are not guaranteed to be described in greater detail here, and are by no means exhaustive. Generally, these fragrance additives belong to different chemical classifications, such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenes, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils, and said fragrance additives may be of natural or synthetic origin. The fragrance base according to the invention is not limited to the above-mentioned fragrance additives, and many of these additives are listed in references such as S. Arctander's *Perfume and Flavor Chemicals*, 1969, Montclair, New Jersey, USA, or later editions thereof, or other works of a similar nature, as well as in the rich patent literature in the field of fragrances. It should also be understood that said additives may also be compounds known to release various types of fragrance compounds in a controlled manner, or may be encapsulated fragrances.

[0092] By "fragrance adjuvant," we mean an ingredient that imparts additional benefits such as color, specific lightfastness, chemical stability, etc. A detailed description of the properties and types of adjuvants commonly used in fragrances is impossible to exhaust, but it must be mentioned that the ingredient is well known to those skilled in the art. However, specific, non-limiting examples include: viscous agents (e.g., surfactants, thickeners, gelling and / or rheology modifiers), stabilizers (e.g., preservatives, antioxidants, heat / light and / or buffers or chelating agents, such as BHT), colorants (e.g., dyes and / or pigments), preservatives (e.g., antibacterial or antimicrobial or antifungal or antiirritant agents), abrasives, skin coolants, fixatives, insect repellents, ointments, vitamins, and mixtures thereof.

[0093] It is understood that those skilled in the art, by applying standard knowledge in the field and by mixing the above-mentioned components of the fragrance composition through trial and error, are fully capable of designing the optimal formulation for the desired effect.

[0094] Other suitable flavor adjuvants that may be used in combination with the compounds of the present invention include tertiary amines, particularly tertiary amines that are highly water-soluble, such as triethanolamine, methyldiethanolamine, dimethylethanolamine, alkyldiethanolamine and ethoxylated alkyldiethanolamine.

[0095] A specific form of the fragrance composition of the present invention relates to a fragrance composition that, in addition to the composition described above, further comprises at least one compound selected from isothiazolones of the following formula:

[0096]

[0097] in

[0098] R 1 and R 2 Each and each independently represents a hydrogen atom, the halogen atom is preferably chlorine, a C1-C4 straight-chain or branched alkyl group, an amino group or a benzylamino group; or, R 1 and R 2 Combined, they represent a phenyl or pyridine ring, which may be substituted with one to four C1-C4 straight-chain or branched alkyl or alkenyl groups and / or one to two halogen atoms, preferably chlorine atoms; and

[0099] R 3 Representing hydrogen atoms, alkali metal atoms, especially Na or K, possibly substituted with one or two halogen atoms and / or one or two methyl, trifluoromethyl, methoxy or amino phenyl or benzyl, amino groups, or possibly substituted with one or two nitrogen, oxygen or halogen atoms, C1-C8 unsaturated straight-chain, branched or cyclic hydrocarbon groups.

[0100] According to a specific embodiment of the present invention, the compound of formula (II) is wherein R 1 and R 2 Compounds that independently represent hydrogen atoms, chlorine atoms, or methyl groups, or, R 1 and R 2 Together they represent a benzene ring, while R 3 Represents a hydrogen atom or a methyl group.

[0101] According to a particular embodiment of the invention, the compound of formula (II) is selected from a group of isothiazolones consisting of: 1,2-benzothiazol-3(2H)-one, 4- or 5-chloro-2-methylisothiazol-3(2H)-one or 2-methylisothiazol-3(2H)-one, or more preferably, 5-chloro-2-methylisothiazol-3(2H)-one or 1,2-benzothiazol-3(2H)-one, and most preferably 1,2-benzothiazol-3(2H)-one.

[0102] In addition to a flavoring composition comprising at least one compound of formula (I), at least one flavor carrier, at least one flavor base and optionally at least one flavor adjuvant, an inventive composition consisting of at least one compound of formula (I) and at least one flavor carrier also represents a specific embodiment of the invention.

[0103] According to a particular embodiment, the above composition comprises more than one compound of formula (I), or in addition to comprising a compound of formula (I), may comprise other compounds that are similar or different in nature from other aromas that are different from those of oct-2-en-4-one, and enable perfumers to prepare blends or fragrances with aroma notes of different compounds of the present invention, thereby creating new structural units for creative purposes.

[0104] For clarity, it should also be understood that any mixture obtained directly from chemical synthesis (where the compounds of the present invention serve as starting materials, intermediates, or end products), such as reaction media that have not been adequately purified, cannot be considered a flavoring composition according to the present invention, provided that the mixture does not provide the compounds of the present invention in a suitable form for use in fragrances. Therefore, unless otherwise stated, unpurified reaction mixtures are generally excluded from the present invention.

[0105] The compound of formula (I) of the present invention can also be advantageously used in all areas of the seasoning or modern fragrance industry (i.e., fine fragrances or functional fragrances) to actively impart a lasting or pleasant strawberry scent to consumer products containing said compound (I).

[0106] Therefore, flavored consumer products containing the following ingredients are also an object of this invention:

[0107] i) at least one compound of formula (I) as defined above, or a flavoring composition, as a flavoring ingredient; and

[0108] ii) Fragrance consumption base.

[0109] The compounds of the present invention may be added as is or as part of the fragrance composition of the present invention.

[0110] For clarity, a "fragrant consumer product" refers to a consumer product that delivers at least one pleasant fragrance effect to the surface or space on which it is applied (e.g., skin, hair, fabric, or household surfaces). In other words, a fragrant consumer product according to the invention is such a product comprising a functional formulation and optional additional benefit agents corresponding to the desired consumer product, and an olfactorily effective amount of at least one compound of the invention. For clarity, the fragrant consumer product is a non-edible product.

[0111] The nature and type of ingredients in scented consumer products are not guaranteed to be described in more detail here, as they are inexhaustible in any way, and those skilled in the art can select them based on their common sense and the characteristics of the product and the desired effect.

[0112] Non-limiting examples of suitable scented consumer products include perfumes, such as fine perfumes, sprays, or eau de perfumes, colognes, shaving lotions, or aftershaves; fabric care products, such as liquid or solid detergents, fabric softeners, liquid or solid fragrance enhancers, fabric fresheners, ironing solutions, paper products, bleach, carpet cleaners, and curtain care products; body care products, such as hair care products (e.g., shampoos, colorants, or hair sprays, color-correcting products, hair styling products, and dental care products), disinfectants, and feminine hygiene products; cosmetic preparations (e.g., skin creams or lotions, cold creams, or deodorants or antiperspirants (e.g., sprays or roll-ons), hair removal products, tanning agents, sunscreens, or after-sun products). Nail products, skin cleansing products, cosmetics; or skin care products (such as soaps, shower mousses, bath oils or shower gels, or hygiene products or foot / hand care products); air care products, such as air fresheners or "ready-to-use" powder air fresheners that can be used in home spaces (rooms, refrigerators, cabinets, shoes or cars) and / or public spaces (lobbies, hotels, shopping malls, etc.); or household care products, such as mold removers, furniture conditioners, wipes, dishwashing liquids or hard surface cleaners (such as floors, bathrooms, sanitary ware or windows); leather care products; car care products, such as polishes, waxes or plastic cleaners.

[0113] Preferred scented compositions or scented products are perfumes, fabric or hard surface detergents, hair care products, and fabric softeners or fresheners.

[0114] Typical examples of fabric detergent or softener compositions into which the compounds of the present invention can be incorporated are described in WO 97 / 34986, or U.S. Patents 4,137,180 and 5,236,615, or EP 799 885. Other typical detergent and softener compositions that can be used are described in publications such as Ullmann's Encyclopedia of Industrial Chemistry, vol. 20, Wiley-VCH, Weinheim, pp. 355-540 (2012); Flick, Advanced Cleaning Product Formulations, Noye Publication, Park Ridge, New Jersey (1989); Showell, in Surfactant Science Series, vol. 71: Powdered Detergents, Marcel Dekker, New York (1988); Proceedings of the World Conference on Detergents (4th, 1998, Montreux, Switzerland), AOCS print.

[0115] The aforementioned consumer product base materials may represent corrosive media for the compounds of this invention, and therefore may require protection against premature decomposition, for example, through encapsulation.

[0116] The compounds according to the invention can be incorporated into various of the above-described articles or compositions in proportions that vary over a wide range of values. When the compounds according to the invention are mixed with flavoring agents, solvents, or additives commonly used in the art, these values ​​depend on the nature of the article to be flavored, the desired sensory effect, and the nature of the auxiliary ingredients in the given base.

[0117] For example, in the case of flavored compositions, the typical concentration of the compound of the present invention is from 0.0001 wt% to 10 wt%, or even higher, based on the weight of the composition to which it is incorporated. Preferably, the concentration is from 0.001 wt% to 5 wt%, more preferably, from 0.001 wt% to 3 wt%, and more preferably, from 0.005 wt% to 1 wt%, based on the weight of the composition to which it is incorporated. In the case of flavored consumer products, the typical concentration of the compound of the present invention is from 0.01 wt% to 5 wt%, or even higher, based on the weight of the consumer product to which it is incorporated.

[0118] As described above, the present invention relates to a method for imparting a persistent or affinity strawberry scent to surfaces such as hard surfaces, fabrics, skin, or hair. Fragrance components that impart a strawberry scent to the environment through evaporation from a surface are generally not very persistent or affinity-based. One reason for this, as mentioned above, is their relatively high volatility, which ensures effective evaporation after surface deposition. Another reason is that typically only a small amount of these compounds are effectively deposited on the surface. This is especially true if they are applied to the surface by a fragrance composition or scented product, and then rinsed off after application. This rinsing step also removes a significant amount of fragrance that should remain on the target surface. Examples of this are detergents and cleaning agents, such as hard surface cleaners, washes, shower gels, shampoos, etc., which are rinsed off after application. Furthermore, fragrance deposition may be insufficient when a surface is scented by contacting it with a fragrance composition or scented product, through a distribution balance between the fragrance composition or scented product and the corresponding surface. Examples of this are conditioning agents or surface fresheners, such as fragrance softeners, which come into contact with the target and are then removed or left to dry. Compounds of formula (I) according to the invention are suitable for enhancing the deposition of fragrances, particularly oct-2-en-4-one, and thus imparting a lasting strawberry scent to surfaces such as hard surfaces, fabrics, skin, or hair.

[0119] Therefore, another aspect of the present invention relates to a method for imparting a lasting or affinity strawberry scent to a surface such as a hard surface, fabric, skin or hair, by adding at least one compound of formula (I) to a scented composition or scented article and applying them to the respective target surface. Detailed Implementation

[0120] Example

[0121] The invention is described in more detail below with reference to the following examples, wherein abbreviations have their usual meanings in the art, and temperatures are expressed in degrees Celsius (°C). NMR spectral data were recorded at 500 MHz in CDCl3 on a Bruker AMX 500 spectrometer. 1 H, recorded at 125.8MHz 13 C (unless otherwise specified), chemical shift d relative to Si(CH3)4 as a standard is expressed in ppm. Coupling constant J is expressed in Hz (br. = broad peak). The reaction is carried out in standard glassware under N2. Commercially available reagents and solvents are used without further purification unless otherwise specified.

[0122] Although a specific conformation or configuration of certain compounds is indicated, this does not imply that the use of these compounds is limited to the said isomers. According to the invention, isomers of all possible conformations or configurations are expected to have similar effects.

[0123] Example 1

[0124] Preparation of compound (I) providing a long-lasting strawberry aroma

[0125] Synthesis of (a)(±)-2-(octylthio)oct-4-one (Compound 1)

[0126] (E)-2-octen-4-one (2.00 g, 15.9 mmol) and 1-octanethiol (2.27 g, 15.5 mmol) were stirred for 2 weeks at room temperature. The residual volatiles were removed by ball-to-ball distillation to give 3.86 g (89%) of a pale yellow oil.

[0127] 1 H-NMR: 3.29–3.21(m,1H),2.70(dd,J=16.7,6.1Hz,1H),2.52(dd,J=16.7,8.0Hz,1H),2.52(t,J=7.4Hz,2 H),2.47–2.35(m,2H),1.62–1.52(m,4H),1.42–1.20(m,15H),0.91(t,J=7.4Hz,3H),0.88(t,J=6.7,3H).

[0128] 13 C-NMR:209.16,50.14,43.40,35.11,31.83,30.88,29.74,29.21,29.20,29.02,25.77,22.66,22.32,21.73,14.10,13.86.

[0129] (b) Synthesis of (±)-2-(dodecylthio)oct-4-one (Compound 2)

[0130] (E)-2-octen-4-one (1.00 g, 7.9 mmol) and 1-dodecylthiol (1.57 g, 7.8 mmol) were stirred at room temperature for 2 weeks. Column chromatography (SiO2, n-heptane, then n-heptane / ethyl acetate 99:1 and 97:3) yielded 1.21 g (46%) of yellow oil.

[0131] 1H-NMR: 3.29–3.21(m,1H),2.70(dd,J=16.7,5.8Hz,1H),2.52(dd,J=16.3,8.0Hz,1H),2.52(t,J=7.5Hz,2H ),2.47–2.35(m,2H),1.61–1.52(m,4H),1.40–1.20(m,23H),0.91(t,J=7.1Hz,3H),0.88(t,J=7.1Hz,3H).

[0132] 13 C-NMR:209.16,50.15,43.40,35.11,31.93,30.88,29.74,29.67,29.65,29 .62,29.55,29.37,29.26,29.03,25.77,22.70,22.32,21.73,14.13,13.86.

[0133] (c) Synthesis of ((4-oxooct-2-yl)thio)propionic acid (Compound 3)

[0134] (E)-2-octen-4-one (4.00 g, 31.7 mmol) and 2-mercaptopropionic acid (thiolactic acid, 3.30 g, 31.1 mmol) were stirred for 23 hours at room temperature. After dilution with methyl tert-butyl ether, the mixture was washed with water and a saturated aqueous solution of NaCl, dried (Na₂SO₄), and concentrated under vacuum (up to 45 °C) to give a crude compound as a yellow oil. Rapid chromatography (SiO₂, n-heptane / methyl tert-butyl ether 9:1 to 1:1) gave 4.99 g (68%) of the yellow oil as a mixture of diastereomers (approximately 1.5:1).

[0135] 1 ¹H-NMR (major isomers): 10.29 (br.s, ¹H), 3.58–3.44 (m, 2H), 2.82 (dd, J = 17.0, 6.1 Hz, ¹H), 2.57 (dd, J = 17.0, 7.4 Hz, ¹H), 2.47–2.35 (m, 2H), 1.61–1.51 (m, 2H), 1.44 (d, J = 7.0 Hz, 3H), 1.36–1.25 (m, 2H), 1.30 (d, J = 7.0 Hz, 3H), 0.91 (t, J = 7.4 Hz, 3H).

[0136] 13 C-NMR (major isomers): 209.14, 179.46, 50.15, 43.28, 40.83, 36.13, 25.74, 22.28, 21.71, 17.34, 13.84.

[0137] Synthesis of (d)(±)-3-((4-oxooct-2-yl)thio)propionic acid (Compound 4)

[0138] As described for compound 3, with (E)-2-octen-4-one (2.00 g, 15.9 mmol) and 3-mercaptopropionic acid (1.65 g, 15.6 mmol), rapid chromatography (SiO2, n-heptane / methyl tert-butyl ether 9:1 to 7:3) yielded 0.39 g (11%) of a yellow oil.

[0139] 1 H-NMR(400MHz):8.24(br.s,1H),3.34–3.22(m,1H),2.84–2.76(m,2H),2.72(dd,J=17.0,5.9Hz,1H),2.70–2.63(m,2H),2.55(dd,J =17.0,7.7Hz,1H),2.41(dt,J=7.4,2.1Hz,2H),1.62–1.51(m,2H),1.37–1.24(m,2H),1.29(d,J=6.7Hz,3H),0.91(t,J=7.3Hz,3H).

[0140] 13 C-NMR(100.6MHz):209.09,177.59,49.93,43.37,35.29,34.66,25.74,25.41,22.29,21.70,13.84.

[0141] Synthesis of (e)(±)-2-methyl-3-((4-oxooct-2-yl)thio)propionic acid (Compound 5)

[0142] As described for compound 3, it was reacted with (E)-2-octen-4-one (2.00 g, 15.9 mmol) and 3-mercapto-2-methylpropionic acid for 45 hours. Spherical-to-spherical distillation (100 °C, 0.4 mbar) was performed to remove residual 2-octen-4-one, followed by rapid chromatographic evaporation (SiO2, n-heptane / methyl tert-butyl ether 9:1 to 1:1) to give 2.47 g (63%) of a yellow oil, which is a mixture of diastereomers (approximately 1:1).

[0143] 1H-NMR:9.26(br.s,1H),3.32–3.22(m,1H),2.92–2.85(m,1H),2.77–2.65(m,2H),2.64–2. 50(m,2H),2.47–2.35(m,2H),1.62–1.51(m,2H),1.37–1.24(m,8H),0.91(t,J=7.4Hz,3H).

[0144] 13 C-NMR:209.13and 209.10,181.11and 181.02,50.01and 50.00,43.39and43.35,40.25and 40.13,35.79and 35.65,33.81and 33.77,25.74,22.29,21.77and 21.71,16.73and 16.61,13.85(q).

[0145] (f)(±)-2-((2-hydroxyethyl)thio)oct-4-one (Compound 6)

[0146] A solution of 2-mercaptoethanol (3.12 g, 39.5 mmol) in tetrahydrofuran (THF, 25 mL) was added dropwise to a solution of (E)-2-octen-4-one (5.37 g, 41.6 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 0.65 mL, 4.3 mmol) in THF (50 mL) at 45–50 °C. After stirring overnight at about 50 °C, the reaction mixture was treated with a mixture of ethyl acetate and an aqueous solution of NaHCO3 (10%). After decantation, the organic layer was washed with a saturated aqueous solution of NaCl, and the aqueous layer was extracted with ethyl acetate. The organic phase was dried (Na2SO4) and concentrated. Sphere-to-sphere distillation (150 °C, 0.056 mbar) gave 7.66 g (90%) of a colorless oil.

[0147] 1 H-NMR:3.82–3.70(m,2H),3.36–3.27(m,1H),2.83–2.68(m,4H),2.56(dd,J=17.0,7.1Hz,1H),2. 47–2.36(m,2H),1.61–1.52(m,2H),1.37–1.27(m,2H),1.30(d,J=6.7Hz,3H),0.91(t,J=7.4,3H).

[0148] 13C-NMR:209.32,61.13,50.00,43.33,34.79,34.11,25.74,22.29,22.13,13.84.

[0149] Synthesis of (g))(2-((4-oxooct-2-yl)thio)ethyl)carbamate (±)-tert-butyl ester (Compound 7)

[0150] As described for compound 6, tert-butyl (2-mercaptoethyl)carbamate (4.62 g, 25.0 mmol) and (E)-2-octen-4-one (3.28 g, 25.4 mmol) in THF (20 mL) and DBU (0.40 mL, 2.6 mmol) in THF (30 mL) were used. Ball-to-ball distillation (170 °C, 0.05 mbar) yielded 7.01 g (87%) of colorless oil.

[0151] 1 H-NMR:4.99(br.s,1H),3.37–3.23(m,3H),2.74–2.60(m,3H),2.54(dd,J=17.0,7.4Hz,1H),2.47–2.35( m,2H),1.61–1.52(m,2H),1.45(s,9H),1.36–1.27(m,2H),1.29(d,J=6.7Hz,3H),0.91(t,J=7.4Hz,3H).

[0152] 13 C-NMR:208.90,155.80,79.36,49.99,43.35,40.02,34.84,31.10,28.40,25.73,22.30,21.89,13.85.

[0153] Synthesis of (h)(±)-2-(dodecylsulfinyl)oct-4-one (Compound 8)

[0154] A solution of (±)-2-(dodecylthio)oct-4-one (1.68 g, 5.1 mmol) in methanol (20 mL) was added to a solution of NaIO4 (1.14 g, 5.3 mmol) in water (11 mL) on an ice bath. The reaction mixture was warmed to room temperature and ethanol (30 mL) was added. The suspension was stirred for 18 hours and then extracted with ethyl acetate (100 mL), washed with saturated aqueous NaCl solution (50 mL), NaHSO3 solution (10%, 50 mL), water (50 mL), saturated aqueous NaHCO3 solution (50 mL), and saturated aqueous NaCl solution (50 mL). The aqueous phases were each extracted again with ethyl acetate (70 mL). The combined organic phases were dried (Na2SO4), filtered, concentrated, and dried under high vacuum for 2 hours. Rapid chromatography (SiO2, n-heptane / ethyl acetate 7:3, then 1:1, then 1:4) gave 0.66 g (37%) of a white solid.

[0155] 1 H-NMR: 3.20(hex.,J=6.8Hz,1H),3.04(dd,J=18.0,6.2Hz,1H),2.71–2.62(m,1H),2.60(dd,J=18.1,7.4Hz,1H),2.56–2.39(m,3H),1.84–1 .65(m,2H),1.62–1.54(m,2H),1.53–1.37(m,2H),1.37–1.19(m,18H),1.23(d,J=7.1Hz,3H),0.91(t,J=7.4Hz,3H),0.88(t,J=7.1Hz,3H).

[0156] 13 C-NMR:207.96,48.92,48.44,43.61,43.11,31.92,29.62(2x),29.54,29. 37,29.34,29.21,28.95,25.83,23.16,22.69,22.28,14.13,13.82,10.45.

[0157] Synthesis of (i)(±)-2-(dodecylsulfonyl)oct-4-one (compound 9)

[0158] A solution of Oxone (2KHSO5 / KHSO4 / K2SO4, 4.71 g, 31.0 mmol) in water (25 mL) was added to a methanol (50 mL) solution of 2-(dodecylthio)oct-4-one (2.09 g, 6.4 mmol). The temperature was brought to 10 °C. The ice bath was removed, and the suspension was stirred for 2 hours. The reaction mixture was extracted with ethyl acetate (100 mL) and washed with saturated aqueous solution of NaCl (50 mL), water (50 mL), saturated aqueous solution of NaHCO3 (50 mL), and saturated aqueous solution of NaCl (50 mL). The aqueous phase was further extracted with ethyl acetate (50 mL) from each phase. The combined organic phases were dried (Na2SO4), filtered, concentrated, and dried under high vacuum for 2 hours. Rapid chromatography (SiO2, n-heptane / ethyl acetate 9:1, then 1:1) gave 1.42 g (62%) of a white solid.

[0159] 1 H-NMR: 3.66–3.57(m,1H),3.18(dd,J=18.1,3.9Hz,1H),2.93(t,J=8.1Hz,2H),2.60(dd,J=18.3,8.7Hz,1H),2.56–2.40(m,2H),1.93–1. 76(m,2H),1.65–1.54(m,2H),1.48–1.39(m,2H),1.39–1.20(m,18H),1.36(d,J=6.7Hz,3H),0.91(t,J=7.4Hz,3H),0.88(t,J=7.4Hz,3H).

[0160] 13 C-NMR:206.86,52.42,50.41,43.10,41.00,31.91,29.60,29.59,29.51,29 .33,29.27,29.07,28.59,25.81,22.69,22.26,21.52,14.49,14.12,13.80.

[0161] Synthesis of (j)(±)-2-(dodecylamino)oct-4-one (Compound 10)

[0162] (E)-2-octen-4-one (1.00 g, 7.9 mmol), 1-dodecylamine (0.98 g, 5.3 mmol), and dimethyl sulfoxide (DMSO, 1 mL) were heated at 50 °C for 5 hours to obtain a crude compound. The sample (1 mL) was removed, washed with water (3 mL), and extracted with ethyl acetate (4 mL). The remaining volatile compounds were removed by ball-to-ball distillation (35 °C, 0.2 mbar) for 2 hours to give 0.5 g of a yellow oil, still containing trace amounts of (E)-2-octen-4-one. The volatiles were then removed directly from the remaining crude compound by ball-to-ball distillation to give another 0.89 g of yellow oil.

[0163] 1 H-NMR:3.16–3.07(m,1H),2.65–2.46(m,3H),2.46–2.35(m,3H),1.63–1.51(m,2H),1.50–1.39( m,2H),1.37–1.20(m,20H),1.06(d,J=6.4Hz,3H),0.90(t,J=7.4Hz,3H),0.88(t,J=6.9Hz,3H).

[0164] 13 C-NMR:210.88,49.91,49.43,47.32,43.39,31.95,30.38,29.70,29.66,29 .65,29.62,29.60,29.38,27.45,25.83,22.71,22.34,20.54,14.13,13.87.

[0165] Synthesis of (k)N,S-bis(4-oxooct-2-yl)-L-cysteine ​​(±)-methyl ester (Compound 11)

[0166] 2-Amino-3-mercaptopropionic acid (R)-methyl ester hydrochloride (L-cysteine ​​methyl ester hydrochloride, 2.23 g, 13.0 mmol), N-ethyl-N-isopropylpropyl-2-amine (1.85 g, 14.3 mmol), and (E)-2-octen-4-one (3.30 g, 26.0 mmol) were dissolved in DMSO (35 mL) and stirred at room temperature for 8 days. The reaction mixture was washed with water (150 mL) and extracted with ethyl acetate (150 mL, 2x). The organic phase was washed with water (50 mL, 3x), dried (Na₂SO₄), and concentrated. It was dried under vacuum (0.5 mbar for 2 h, then at 50 °C for 15 min) to give an orange oil. Rapid chromatography (SiO2, n-heptane / ethyl acetate 9:1 to 4:1) and drying under high vacuum (0.07 mbar, 30 °C for 2 h) yielded 1.63 g (32%) of an orange-yellow oil (a mixture of diastereomers).

[0167] 1 H-NMR:3.75(t,J=1.8Hz,3H),3.54and 3.49(q,J=6.6and 6.4Hz,1H),3.34–3.23(m,1H),3.18–3.09(m,1H),2.84–2.75(m,2H),2.75–2.66(m,1H),2.60and 2.57(dd,J=7.7and 6.1Hz,1H),2.55–2.46(m,2H),2.46–2.34(m,4H),1.93(br.s,1H),1.60–1.50(m,4H),1.36–1.24(m,7H),1.06(m,3H),0.94–0.87(m,6H).

[0168] 13 C-NMR:210.32,210.29,210.04,208.72,174.54,174.52,174.03,174.02,59.52,5 9.40,58.83,58.73,52.13,52.00,50.33,49.96,49.93,49.92,48.58,48.57,47.61 ,43.50,43.48,43.34,43.31,43.20,35.77,35.74,35.57,35.54,34.31,34.27,34.24,25.75,22.32,22.30,21.66,21.64,21.21,21.20,20.21,20.19,13.88,13.86.

[0169] Synthesis of (l)(±)-2-(benzyloxy)oct-4-one (Compound 12)

[0170] 1,1,3,3-Tetramethylguanidine (4.95 g, 43.0 mmol) was added to a solution of (E)-2-octen-4-one (27.00 g, 214.0 mmol) in benzyl alcohol (69.40 g, 642.0 mmol). The reaction mixture was stirred at 40 °C for 40 h. Vacuum distillation (0.08 mbar, 80–109 °C) gave 33.26 g (66%) of a pale yellow oil.

[0171] 1 H-NMR:7.37–7.23(m,5H),4.55(d,J=11.5Hz,1H),4.44(d,J=11.5Hz,1H),4.09–4.00(m,1H),2.77(dd,J=15.7,7 .4Hz,1H),2.48–2.35(m,3H),1.58–1.50(m,2H),1.35–1.24(m,2H),1.23(d,J=6.1Hz,3H),0.89(t,J=7.4Hz,3H).

[0172] 13 C-NMR:209.72,138.56,128.33,127.70,127.54,71.77,70.91,49.89,43.73,25.65,22.28,19.92,13.86.

[0173] (m) Synthesis of undeceno-10-enoic acid (±)-4-oxooct-2-yl ester (Compound 13)

[0174] (i) 4,5-Dichloro-3,6-dioxocyclohexyl-1,4-diene-1,2-dionitrile (DDQ, 11.60 g, 51.2 mmol) and water (20 mL) were added to a solution of (±)-2-(benzyloxy)oct-4-one (compound 12, 10.00 g, 42.7 mmol, prepared as previously described) in dichloromethane (180 mL). After 6 hours, the mixture was subjected to… Filtration. The filtrate was washed with saturated aqueous solution of NaHCO3 (50 mL) and NaCl (2 × 50 mL). The organic phase was dried (Na2SO4) and filtered. The solvent was evaporated and the residue was purified by column chromatography (SiO2, n-heptane / ethyl acetate 95:5 to 70:30 to 50:50) to give 3.89 g (63%) of (±)-2-hydroxyoct-4-one as an orange oil.

[0175] 1H-NMR(400MHz):4.28–4.16(m,1H),3.23(d,J=2.8Hz,1H),2.60(dd,J=17.6,3.2Hz,1H),2.51(dd,J=17.5,8.7Hz ,1H),2.42(t,J=7.4Hz,2H),1.62–1.51(m,2H),1.38–1.24(m,2H),1.19(d,J=6.4Hz,3H),0.91(t,J=7.4Hz,3H).

[0176] 13 C-NMR(100.6MHz):212.46,63.89,50.45,43.31,25.71,22.37,22.28,13.83.

[0177] (ii) At room temperature, 10-undecyl chloride (2.32 g, 11.4 mmol) was added to a stirred solution of (±)-2-hydroxyoct-4-one (1.50 g, 10.4 mmol), 4-dimethylaminopyridine (DMAP, 1.67 g, 13.7 mmol), and triethylamine (1.37 g, 13.5 mmol) in dichloromethane (30 mL). The reaction mixture was stirred at room temperature for 30 hours, then poured into an aqueous HCl solution (10%, 30 mL), extracted with diethyl ether (30 mL), and washed with a saturated aqueous NaCl solution (30 mL), NaHCO3 (30 mL), and NaCl (2 x 30 mL). The organic phase was dried (Na2SO4), filtered, and concentrated. Repeated column chromatography (SiO2, n-heptane / ethyl acetate 90:10 and 95:5) yielded 1.23 g (38%) of undecano-10-enoic acid (±)-(1-methyl-3-oxo-heptyl) ester as a colorless oil.

[0178] 1 H-NMR: 5.86–5.75(m,1H),5.29(m,1H),5.03–4.90(m,2H),2.77(dd,J=16.0,7.4Hz,1H),2.52(dd,J=16.0,6.1Hz,1H),2.41(t,J=7. 4,2H),2.24(t,J=7.5Hz,2H),2.07–2.00(m,2H),1.63–1.50(m,4H),1.41–1.23(m,12H),1.26(d,J=6.4Hz,3H),0.90(t,J=7.4,3H).

[0179] 13C-NMR:207.87,173.04,139.17,114.15,66.94,48.58,43.09,34.53,33.7 9,29.29,29.21,29.08,29.06,28.90,25.67,24.96,22.28,20.11,13.85.

[0180] Synthesis of (n)2-((4-oxooct-2-yl)thio)acetic acid(±)-2-ethylhexyl ester (Compound 14)

[0181] (E)-2-octen-4-one (3.00 g, 23.8 mmol) and 2-ethylhexyl 2-mercaptoacetic acid (4.86 g, 23.8 mmol) were stirred at room temperature for 24 days. Column chromatography (SiO2, n-heptane / ethyl acetate 90:10) yielded 0.57 g (7%) of a pale yellow oil, a mixture of diastereomers.

[0182] 1 H-NMR:4.09–4.00(m,2H),3.45–3.34(m,1H),3.32–3.24(m,2H),2.77(dd,J=17.0,5.8Hz,1H),2.55(dd,J=17.0,8 .0Hz,1H),2.46–2.35(m,2H),1.65–1.51(m,3H),1.42–1.23(m,16H),0.91(t,J=7.4Hz,3H),0.90(t,J=7.4Hz,3H).

[0183] 13 C-NMR:208.50,170.81,67.83,49.73,43.16,38.74,36.03,33.02,30.32,30 .31,28.90,25.76,23.69,22.97,22.31,21.18,14.05,13.85,10.95,10.94.

[0184] (o) Synthesis of bis(2-((4-oxooct-2-yl)thio)acetic acid)(±)-ethane-1,2-dimethyl ester (Compound 15)

[0185] (E)-2-octen-4-one (3.00 g, 23.8 mmol) and bis(2-mercaptoacetic acid) ethane-1,2-diyl ester (2.30 g, 10.9 mmol) were stirred for 72 hours at room temperature. Continuous column chromatography (SiO2, initially toluene / methyl tert-butyl ether (MTBE) 90:10, then from pure toluene to toluene / MTBE 90:10) and drying under high vacuum (3 h) yielded 3.06 g (60%) of a pale yellow oil, a mixture of diastereomers containing approximately 6% 2-((4-oxooct-2-yl)thio)acetic acid 2-(2-mercaptoacetoxy)ethyl ester.

[0186] 1 H-NMR:4.36(s,4H),3.47–3.37(m,2H),3.36–3.28(m,4H),2.81–2.73(m,2H),2.56(dd,J=17.0,7.7Hz,2H ),2.47–2.35(m,4H),1.60–1.51(m,4H),1.36–1.27(m,4H),1.30(d,J=7.1Hz,6H),0.91(t,J=7.4Hz,6H).

[0187] 13 C-NMR:208.45,170.37,62.84,49.63,43.17,35.97,32.70,25.73,22.29,21.23,13.85.

[0188] Example 2

[0189] Performance of fabric softener base materials containing compounds of formula (I) of the present invention

[0190] The persistent strawberry scent produced by the compound of formula (I) of the present invention was tested in a fabric-softening surfactant emulsion having the following final composition:

[0191]

[0192] a) Headspace measurement

[0193] In a flask, a solution (0.1 mL) of one of the compounds of formula (I) of the present invention described in Example 1 in ethanol (10 mL) was added to a fabric softener (0.07 g) in water (0.90 mL). After homogenization, the sample was diluted with softened cold tap water (23.3 mL). A piece of cotton fabric (EMPA cotton test cloth Nr. 221, source: Material (prüfanstalt), pre-washed with unscented detergent powder and cut into pieces of approximately 15 x 15 cm (approximately 5.2 g), was manually stirred for 3 minutes, allowed to stand for 2 minutes, then wrung out by hand and weighed (approximately 10.0 g) to obtain a constant amount of residual water. A reference sample (0.1 mL) consisting of an equimolar amount of unmodified (E)-2-octen-4-one (0.055 mmol) in ethanol (10 mL) was added to fabric softener (0.07 g) in water (0.90 mL) and analyzed in the same manner. The cotton sheets were air-dried for 1 or 3 days prior to analysis. For measurements, the sheets were placed in a headspace sample cell (internal volume approximately 160 mL), kept at 25 °C, and exposed to a constant airflow of approximately 200 mL / min. The air was filtered through activated carbon and aspirated through a saturated NaCl aqueous solution (to ensure a constant humidity of approximately 75%). The system reaches equilibrium within 15 minutes, while simultaneously adsorbing volatiles onto the waste. Filter cartridge (containing 100mg) The volatiles were then transferred to a clean TA adsorption resin seven times consecutively. Adsorb on the filter cartridge for 15 minutes, then remove from waste Adsorption on the filter cartridge for 45 minutes. Alternatively, after equilibrating the system for 135 minutes, adsorb the volatiles onto the waste. Record a data point on the filter cartridge. Then, place the volatiles in a clean container. Adsorption was performed on the filter cartridge for 15 minutes. Waste cartridges were discarded; remaining cartridges were desorbed onto a Perkin Elmer TurboMatrix ATD desorber connected to an Agilent Technologies 7890A gas chromatograph equipped with an HP-1 capillary column (30 m, 0.32 μm inner diameter, 0.25 μm membrane) and an FID detector. Volatiles were analyzed using a temperature gradient from 60 °C to 220 °C at 15 °C / min. Headspace concentrations (in ng / L air) were obtained by external standard calibration using different concentrations of the fragrance to be released in ethanol. Each calibration solution (0.2 mL) was injected into a clean container. The sample was placed in a filter cartridge and then desorbed and analyzed under the same conditions. Table 1 summarizes the evaporation results of (E)-2-octen-4-one after a total sampling time of 150 minutes on a dry cotton cloth, after drying for 1 day and 3 days. All data are averages of at least two measurements.

[0194] Table 1 The average headspace concentration of (E)-2-octen-4-one was measured 150 minutes after the sample was taken from the dry cotton cloth after 1 day and 3 days of drying.

[0195]

[0196] Compared to the reference sample, the compound according to formula (I) releases at least an equal but mostly higher amount of (E)-2-octen-4-one into the top space above the dry cotton fabric. Therefore, the compound of formula (I) according to the invention is able to impart a lasting strawberry scent to the surface of the cotton fabric.

[0197] b) Sensory evaluation

[0198] Cotton towels (30 towels, 18cm x 18cm, approximately 30g each) were washed in a European washing machine (Miele Novotronic W300-33CH) at 40°C using a short cycle with 30g of unscented detergent. After washing, they were rinsed at 900rpm with 12.7g of the concentrated fabric softener containing compound 2 or an equimolar amount of (E)-2-octen-4-one. The towels were then air-dried for 24 hours and then evaluated by a panel of 20 trained members. The members were asked to rate the odor intensity of the towels on a scale of 1 to 7, where 1 corresponds to no odor and 7 corresponds to a very strong odor.

[0199] The results are shown in Table 2 below.

[0200] Table 2 Odor properties in fabric softener applications

[0201]

[0202] The performance of dry fabrics from which (E)-2-octen-4-one is released from the compounds of the present invention is superior to that of (E)-2-octen-4-one, especially after 3 days. Therefore, the compounds of formula (I) according to the present invention can impart a lasting strawberry odor, confirming the above-described headspace analysis reported in Table 1.

[0203] Example 3

[0204] Performance of general hard surface cleaner formulations containing compounds of inventive formula (I)

[0205] A persistent strawberry scent produced by the compound of formula (I) of the present invention was tested in a general-purpose surface cleaner (APC). An APC formulation having the following final composition has been prepared:

[0206] In a flask, one compound of formula (I) of the present invention (0.0369 mmol) was dissolved in ethanol (100 μm). Then, APC formulation (3.0 g) was added, and the sample was gently shaken. Aliquots (1 mL) of these samples were transferred and diluted with softened tap water (9 mL). A membrane (0.75 mL) of this solution was aspirated onto a porous ceramic plate (approximately 5 × 10 cm), covered with a crystallizing dish (2.5 L), and allowed to stand at room temperature. Similarly, a reference sample was prepared consisting of unmodified (E)-2-octen-4-one (0.0369 mmol) instead of one compound of formula (I) of the present invention in ethanol (100 μm) and treated in the same manner.

[0207] One day later, each ceramic plate was placed in a headspace sampler (approximately 625 mL) and exposed to a constant airflow of approximately 200 mL / min. The air was filtered through activated carbon and aspirated through a saturated NaCl aqueous solution (to ensure a constant humidity of approximately 75%). This process was achieved by adsorbing volatiles onto the waste... On the filter cartridge, equilibrate the headspace system for 15 minutes. Then, alternately adsorb volatiles onto clean filters. 10 minutes on the filter cartridge, then adsorb onto the waste. Filter cartridge (6x) for 20 minutes. Discard the waste cartridge; desorb the cleaned cartridge as described in Example 2 and perform analysis. All measurements were performed at least twice. The average headspace concentrations of (E)-2-octen-4-one released from the compound of formula (I) prepared in Example 1 or from the reference sample after 115 minutes of sampling on a porous ceramic plate are listed in Table 3. Table 3 also shows the fold increase in (E)-2-octen-4-one released from the compound of formula (I) of the present invention relative to the reference sample.

[0208] Table 3 The average headspace concentration of (E)-2-octen-4-one measured after 115 minutes of sampling in an APC application above a ceramic plate, and the multiple of increase in headspace concentration released from the compound of formula (I) of the present invention relative to a reference sample.

[0209]

[0210] One day later, the compound of formula (I) prepared in Example 1 released more (E)-2-octen-4-one into the headspace than the reference sample. Therefore, through APC application, the compound of formula (I) of the present invention can provide a long-lasting and pleasant strawberry scent to hard surfaces.

[0211] Example 4

[0212] Performance of hair conditioning formulations containing compounds of formula (I) of the present invention

[0213] In hair conditioning applications, the long-lasting strawberry scent produced by the compound of formula (I) of the present invention was tested. A hair conditioning formulation having the following final composition has been prepared:

[0214]

[0215] A solution of compound (I) of the present invention in ethanol was prepared by accurately weighing 0.4 mmol of the compound into a volumetric flask (5 mL) and filling it with ethanol. Similarly, a reference solution containing an equimolar amount of (E)-2-octen-4-one was prepared.

[0216] Weigh the above hair conditioner formulation (920 mg) into a sample tube (3 mL), and then add one of the compounds of formula (I) or (E)-2-octen-4-one (reference) of the present invention to an ethanol solution (100 μL). Seal the test tube, shake (50x), and centrifuge manually (approximately 3500 rpm) for 30 seconds.

[0217] A Caucasian hair sample (source: Kerling International Haarfabrik GmbH, approximately 10 cm long, approximately 0.5 g) was rinsed and rubbed for 30 seconds under running water at 37°C at a flow rate of 2 L / min, and excess water was squeezed out with fingertips. Unscented shampoo (0.1 g) was applied to the hair sample and washed for 30 seconds. The shampoo was then rinsed under running water at 37°C for 30 seconds, and excess water was squeezed out with fingertips. A hair conditioning formula (0.1 g) containing a compound of formula (I) of this invention or (E)-2-octen-4-one as a reference was then applied to the hair sample. The hair sample was gently rubbed between fingertips for 1 minute, combed once, and air-dried.

[0218] Six hours later, the comb (10x) was applied and secured with tape to a constant-temperature (25°C) headspace sample inlet with an internal volume of approximately 165 mL. Air was pumped through the sample at a constant flow rate (200 mL / min). The incoming air was filtered through activated carbon and a saturated NaCl aqueous solution. Volatile substances were absorbed into the waste... Place the filter cartridge on the filter and allow the system to balance for 10 minutes. Then, place the volatiles in the first clean filter cartridge. Adsorb on the filter cartridge for 10 minutes, then on the second clean cartridge. The hair sample was adsorbed onto the filter cartridge for 10 minutes. Then, the pump stopped. The hair sample remained in the headspace sampling cell without being connected to the filter cartridge. 24 hours later, the waste sample was connected... Turn on the pump and balance the system for 10 minutes. Then continuously adsorb the volatiles for 10 minutes to two clean filters. On the filter cartridge. Discard the waste cartridge; desorb the cleaned filter cartridge as described in Example 2 and analyze it. All measurements should be performed at least twice.

[0219] The average headspace concentrations of (E)-2-octen-4-one released from the compound of formula (I) prepared in Example 1 or the reference sample (desorbed from the first cartridge) after 6 hours and 24 hours are listed in Table 4. Table 4 also shows the fold increase in (E)-2-octen-4-one released from the compound of formula (I) of the present invention relative to the reference sample.

[0220] Table 4 The mean headspace concentration of (E)-2-octen-4-one measured in hair conditioning applications on hair samples at 6 hours and 24 hours, and the multiple of increase in headspace concentration released from the compound of formula (I) of the present invention relative to a reference sample.

[0221]

[0222] After 6 hours and 24 hours, the compound of formula (I) prepared in Example 1 released more (E)-2-octen-4-one into the headspace than the reference sample. Therefore, through hair conditioning application, the compound of formula (I) of the present invention can provide hair with a long-lasting and pleasant strawberry scent.

[0223] Example 5

[0224] Preparation of liquid detergents comprising the compounds of the present invention

[0225] Table 5 Composition of liquid detergent formulation

[0226]

[0227] 1) Hostapur SAS 60; Source: Clariant

[0228] 2) Edenor K 12-18; Source: Cognis

[0229] 3) Genapor LA 070; Source: Clariant

[0230] 4) Source: Genencor International

[0231] 5) Aculyn 88; Source: Dow Chemical

[0232] The liquid detergent was prepared by adding compound 2 of the present invention in an amount of 0.01 to 5% (by weight), preferably 0.5 to 1.5% (by weight), relative to the total weight of the liquid detergent, to the unscented liquid detergent formulation in Table 5 under gentle shaking.

[0233] Example 6

[0234] Preparation of a transparent homogeneous shampoo comprising the composition of the present invention

[0235] Table 6 Composition of a transparent homogeneous shampoo formula

[0236]

[0237] 1) Ucare Polymer JR-400, Source: Noveon

[0238] 2) Source: Schweizerhall

[0239] 3) Glydant, Source: Lonza

[0240] 4) Texapon NSO IS, Source: Cognis

[0241] 5) Tego Betain F 50, Source: Evonik

[0242] 6)Amphotensid GB 2009, source: Zschimmer&Schwarz

[0243] 7) Monomuls 90L-12, Source: Gruenau

[0244] 8) Sodium Niparaginase, Source: NIPA

[0245] A shampoo was prepared by dispersing polyquaternium-10 in water. The remaining components of phase A were added one by one, mixing thoroughly after each addition. This premix was then added to the polyquaternium-10 dispersion and mixed for another 5 minutes. Next, premixed phases B and C (Monomuls 90L-12 melted in Texapon NSO IS by heating) were added while stirring. Phases D and E were added while stirring. The pH was adjusted to 5.5–6.0 with citric acid solution to obtain an unscented shampoo formulation.

[0246] A scented shampoo was prepared by adding compound 2 of the present invention in an amount of 0.01 to 5% (by weight), preferably 0.5 to 1.5% (by weight), relative to the total weight of the shampoo, to the unscented shampoo formulation in Table 6 under gentle shaking.

[0247] Example 7

[0248] Preparation of Structured Shower Gel Containing the Composition of the Invention

[0249] Table 7: Composition of shower gel formula

[0250] Element Quantity (% by weight) Deionized water 49.350 <![CDATA[Sodium EDTA 1) > 0.050 <![CDATA[Acrylate copolymer 2) > 6.000 <![CDATA[Sodium C12 - C15 alcohol polyether sulfate 3) > 35.000 20% sodium hydroxide aqueous solution 1.000 <![CDATA[Cocamidopropyl betaine 4) > 8.000 <![CDATA[Methylchloroisothiazolinone and Methylisothiazolinone 5) > 0.100 Citric acid (40%) 0.500

[0251] 1) ETETA B powder; Trademark and source: BASF

[0252] 2) CARBOPOL AQUA SF-1 polymer; trademark and source: NOVEON

[0253] 3) ZETESOL AO 328U; Trademark and source: ZSCHIMMER & SCHWARZ

[0254] 4) TEGO-BETAIN F 50; Trademark and source: GOLDSCHMIDT

[0255] 5) KATHON CG; Trademark and source: ROHM & HASS

[0256] The shower gel was prepared by adding 0.01 to 5% (by weight), preferably 0.5 to 1.5% (by weight), of the compound 2 of the present invention relative to the total weight of the shower gel to the unscented shower gel formulation in Table 7 under gentle shaking.

[0257] Example 8

[0258] Preparation of a transparent shower gel containing the composition of the present invention

[0259] Table 8 Composition of the transparent shower gel formula

[0260] Element Concentration (% by weight) Deionized water 52.40 <![CDATA[Sodium EDTA 1) > 0.10 Sodium benzoate 0.50 Propylene glycol 2.00 <![CDATA[Sodium C12-C15 alcohol polyether sulfate 2) > 35.00 <![CDATA[Cocamidopropyl betaine 3) > 8.00 <![CDATA[Polyquaternium-7 4) > 0.20 Citric acid (40%) 1.00 Sodium chloride 0.80

[0261] 1) ETETA B powder; Trademark and source: BASF

[0262] 2) ZETESOL AO 328U; Trademark and source: ZSCHIMMER & SCHWARZ

[0263] 3) TEGO-BETAIN F 50; Trademark and source: GOLDSCHMIDT

[0264] 4) MERQUAT 550; Trademark and source: LUBRIZOL

[0265] A transparent shower gel is prepared by adding 0.01 to 5% (by weight), preferably 0.5 to 1.5% (by weight), of the compound 2 of the present invention relative to the total weight of the shower gel to the unscented shower gel formulation in Table 8 under gentle shaking.

[0266] Example 9

[0267] Preparation of a milky shower gel containing the composition of the present invention

[0268] Table 9 Composition of a creamy body wash formula

[0269] Element Concentration (% by weight) Deionized water 50.950 <![CDATA[Sodium EDTA 1) > 0.050 Sodium benzoate 0.500 86% glycerin 3.500 <![CDATA[Sodium dodecyl polyoxyethylene sulfate 2) > 27.000 <![CDATA[Polyquaternium-7 3) > 1.000 <![CDATA[Coco - Betaine 4) > 6.000 <![CDATA[Methyl Gluceth-120 Trioleate 5) > 1.000 Citric acid (40%) 1.000 <![CDATA[Ethylene glycol distearate & Laureth-4 & Cocamidopropyl betaine 6) > 3.000 Sodium chloride 20% 5.000 <![CDATA[PEG-40 Hydrogenated Castor Oil 7) > 1.000

[0270] 1) ETETA B powder; Trademark and source: BASF

[0271] 2) Texapon NSO IS; Trademark and source: COGNIS

[0272] 3) MERQUAT 550; Trademark and source: LUBRIZOL

[0273] 4) DEHYTON AB-30; Trademark and source: COGNIS

[0274] 5) GLUCAMATE LT; Trademark and source: LUBRIZOL

[0275] 6) EUPERLAN PK 3000AM; Trademark and source: COGNIS

[0276] 7) CREMOPHOR RH 40; Trademark and source: BASF

[0277] A transparent shower gel is prepared by adding 0.01 to 5% (by weight), preferably 0.5 to 1.5% (by weight), of the compound 9 of the present invention relative to the total weight of the shower gel to the unscented shower gel formulation in Table 8 under gentle shaking.

[0278] Example 10

[0279] Preparation of a hand-washing dishwashing detergent containing the composition of the present invention

[0280] Table 10 Composition of hand dishwashing detergent formula

[0281] Element Quantity (% by weight) <![CDATA[Linear alkylbenzene sulfonic acid (1) > 20 <![CDATA[Diethanolamide (2) > 3.5 <![CDATA[Sodium hydroxide (50%) (3) > 3.4 <![CDATA[Secondary alcohol ethoxolate (4) > 2.5 Sodium xylenesulfonate 6.3 water 64.3

[0282] 1) Biosoft Trademark and source: Stepan Company

[0283] 2) Ninol Trademark and source: Stepan Company

[0284] 3) Stepanate Trademark and source: Stepan Company

[0285] 4) Tergitol Trademark and source: Dow Chemical Company

[0286] Mix water with sodium hydroxide and diethanolamide. Add LAS. Neutralize the LAS, then add the remaining ingredients. Check the pH (=7-8) and adjust if necessary.

[0287] A scented hand dishwashing detergent is prepared by adding compound 2 of the present invention in an amount of 0.01 to 5% (by weight), preferably 0.5 to 1.5% (by weight), relative to the total weight of the hand dishwashing detergent, to the unscented hand dishwashing detergent formulation in Table 10 under gentle shaking.

Claims

1. A compound of formula (I), in n represents an integer from 1 to 2; A represents C2 to C with n valences. 22 The hydrocarbon group optionally includes one or two functional groups selected from the group consisting of alcohols, esters, carboxylic acids, amines, amides, or thiols; and X represents a group from formulas (i) to (vi). In the formula, the wavy line indicates the position of the bond between carbon 2 and X, the shaded line indicates the position of the bond between X and A, and R independently represents a hydrogen atom or a straight-chain or branched hydrocarbon group from C1 to C4, provided that the shaded line is not directly connected to a heteroatom or carbonyl functional group of A, and that 2-(propylthio)oct-4-one, 4-(benzyloxy)benzoic acid 4-oxooct-2-yl ester, 2-(methoxymethoxy)oct-4-one, 2-((2-methoxyethoxy)methoxy)oct-4-one, 2-(ethylamino)oct-4-one and 2-(benzylamino)oct-4-one.

2. The compound according to claim 1, characterized in that, X represents the group of formula (i) to (iv) or (vi).

3. The compound according to claim 2, characterized in that, X represents the group in formula (i).

4. The compound according to claim 1, characterized in that, A represents C2 to C with n valences. 18 A hydrocarbon group, which optionally contains one or two functional groups selected from the group consisting of alcohols, esters, carboxylic acids, or amines.

5. The compound according to claim 4, characterized in that, This ester is a carbamate.

6. The compound according to claim 1, characterized in that, n is 1.

7. The compound according to claim 1, characterized in that, The compound is 2-(alkylthio)oct-4-one, 2-(alkylsulfinyl)oct-4-one, 2-(alkylsulfonyl)oct-4-one, or a 4-oxooct-2-yl ester of an alkyl or olefinic acid, wherein the alkyl or alkenyl group is C6 or C7. 18 The changes between them.

8. Use of the compound of formula (I) according to claim 1, as a flavoring ingredient to provide a lasting strawberry scent to the environment.

9. The use according to claim 8, characterized in that, The compound of formula (I) is used in combination with at least one of the following: oct-2-en-4-one, 2,5-dimethyl-4-hydroxy-2H-furan-3-one, 5-ethyl-4-hydroxy-2-methyl-3(2H)-furanone, 2,5-dimethyl-4-oxo-4,5-dihydrofuran-3-yl acetate, ethyl 3-methyl-3-phenylethylene oxide-2-carboxylate, ethyl 3-phenylethylene oxide-2-carboxylate, methyl 2-acetaminobenzoate or 3-phenylpropyl 3-methylbutyrate, 2-methyl-4-oxo-4H-pyran-3-yl propionate, 2-methylpent-2-enoic acid or (2S,5S)-2-(tert-butyl)-5-methyl-2-propyltetrahydrofuran.

10. A method for imparting, enhancing, improving or altering the strawberry odor characteristics of a flavored composition or flavored article, the method comprising adding an effective amount of at least one compound of formula (I) according to claim 1 to the composition or article.

11. A flavoring composition comprising: i) at least one compound of formula (I) as defined in claim 1 as a flavoring ingredient; ii) at least one ingredient selected from the group consisting of a flavor carrier and a flavor base; and iii) Optionally, at least one flavoring adjuvant.

12. The flavoring composition according to claim 11, characterized in that, It also contains at least one compound selected from isothiazolone of formula (II): Where R 1 and R 2 Each and each independently represents a hydrogen atom, a halogen atom, a C1-C4 straight-chain or branched alkyl group, an amino group, or a benzylamino group; or, R 1 and R 2 Combined, they represent a phenyl or pyridine ring, which may be substituted with one to four C1-C4 straight-chain or branched alkyl or alkenyl groups and / or one to two halogen atoms; and R 3 Represents a hydrogen atom, an alkali metal atom, possibly substituted with one or two halogen atoms and / or one or two methyl, trifluoromethyl, methoxy or amino phenyl or benzyl, amino groups, or possibly substituted with one or two nitrogen, oxygen or halogen atoms, C1-C8 unsaturated straight-chain, branched or cyclic hydrocarbon groups.

13. The flavoring composition according to claim 12, characterized in that, The halogen atom is chlorine.

14. The flavoring composition according to claim 12, characterized in that, The alkali metal atom is either Na or K.

15. A scented consumer product comprising: i) at least one compound of formula (I) as defined in claim 1 or a flavoring composition as defined in claim 11 as a flavoring ingredient; and ii) Fragrance consumption base.

16. The scented consumer product according to claim 15, characterized in that, The scented consumer product is a perfume, fabric care product, body care product, air care product, or home care product.

17. The scented consumer product according to claim 15, characterized in that, The scented consumer product is a fine perfume, liquid or solid detergent, fabric softener, fabric freshener, ironing solution, shampoo, coloring agent, hair spray, deodorant or antiperspirant, soap, bath mousse, bath oil or shower gel, hygiene product, or air freshener.

18. The scented consumer product according to claim 17, characterized in that, This air freshener is a "ready-to-use" powder air freshener.

19. The scented consumer product according to claim 17, characterized in that, This liquid or solid detergent is a hard surface cleaner.

20. A method of imparting a lasting or affinity strawberry scent to a surface such as a hard surface, fabric, skin or hair, by adding at least one compound of formula (I) according to claim 1 to a scented composition or scented article and applying them to the respective target surface.

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