Thiazolidine-4-carboxylate properfumes

Abstract

The present invention relates to compounds of formula (I) as properfume compounds. In particular, the present invention relates to a method to release an aldehyde or a ketone of formula (II), by exposing the compound of formula (I) to a trace of water. Moreover, the present invention relates to a perfuming composition and a perfumed consumer product comprising at least one compound of formula (I).

Description

[0001] THIAZOLIDINE-4-CARBOXYLATE PROPERFUMES

[0002] Technical Field

[0003] The present invention relates to compounds of formula (I) as properfume compounds. In particular, the present invention relates to a method to release an aldehyde or a ketone of formula (II), by exposing the compound of formula (I) to a trace of water. Moreover, the present invention relates to a perfuming composition and a perfumed consumer product comprising at least one compound of formula (I).

[0004] Background

[0005] The perfume industry has a particular interest for compositions or additives which are capable of prolonging or enhancing the perfuming effect of at least one perfuming ingredient for a certain period of time. It is particularly desirable to obtain long-lasting properties for standard perfumery raw materials which are too volatile or have a poor substantivity by themselves, or which are only deposited in a small amount onto the surface of the final application. Furthermore, some of the perfumery ingredients are unstable and need to be protected against slow degradation prior to their use. Long-lasting perfumes are desirable for various applications, as for example fine or functional perfumery or cosmetic preparations. The washing and softening of textiles are particular fields in which there is a constant need to enable the effect of active substances, in particular perfumes, or perfuming compositions, to be effective for a certain period of time after washing, softening and drying. Indeed, many active substances which are particularly suitable for this type of application are known to lack tenacity on laundry, or do not remain on the laundry when rinsed, with the result that their perfuming effect is experienced only briefly and not very intensely. Given the importance of this type of application in the perfume industry, research in this field has been sustained, in particular with the aim of finding new, and more effective solutions to the aforementioned problems.

[0006] Furthermore, consumers increasingly demand eco-friendly and sustainable solutions for the aforementioned problems. This implies that compositions or additives used to prolong or enhance the perfuming effect must be biocompatible and highly biodegradable. Furthermore, substrates and building blocks that serve to improve the long-lastingness of perfumery materials or other active compounds should be derived from natural sources, consisting of renewable carbon. Derivatives of naturally occurring amino acids are examples for suitable substrates or building blocks in this context.

[0007] WO 2019 / 121269 describes the use of oxazolidine- or thiazolidine-carboxylic acid compounds in deodorant compositions to suppress the formation of human body malodor. The compounds inhibit the Staphylococcus hominis C-S beta-lyase of microorganisms present on human skin and thus prevent the generation of 3-methyl-3-sulfanylhexan-l-ol, which is a potent malodor component. The document does not suggest that oxazolidine- or thiazolidine- carboxylic acids can be cleaved to release active aldehydes or ketones and thus provide a long-lasting perfuming effect.

[0008] WO 00 / 72816 relates to the use of aldehyde- and ketone- releasing properfume accords comprising heterocyclic profragrances, beta-amino profragrances and / or orthoester proaccords. Among the heterocyclic profragrances, oxazolidines are described as the preferred aldehyde- or ketone-releasing structures. To achieve an enhanced fragrance benefit to fine fragrances, personal care and hygiene articles, fragrance delivery systems composed of at least two of the oxazolidine profragrances, beta-amino profragrances and / or orthoester proaccords are used. The biocompatibility, and in particular the desired high degree of biodegradation, of the properfumes has not been addressed in this document.

[0009] It has now surprisingly been found that highly biodegradable thiazolidine-4- carboxylate derivatives of formula (I) according to the present invention may be efficiently prepared from the naturally occurring amino acid cysteine, and that these compounds allow the release of an aldehyde or ketone compound of formula (II).

[0010] Detailed description

[0011] Olfaction is a complex and dynamic process and controlling the release profile of volatile fragrance compounds may maximize the impact of fragrance formulations and enrich the sensorial experience. Properfumes, such as the compounds of the present invention, add a dimension of control and long-lastingness to the release profile of highly volatile perfumery raw materials (PRMs), such as aldehydes or ketones representing an important group of compounds in the perfumery field.

[0012] Without intending to be limited to any particular theory, the compounds of the present invention may achieve their effect on the olfactive properties of a perfuming composition by tethering the PRM to a molecular anchor and requiring a specific reaction mechanism under certain environmental conditions to release the volatile PRM from this anchor. In the present invention, the release of one, two or up to three PRMs is prompted by hydrolysis when the properfume is exposed to humidity in ambient air.

[0013] A first object of the present invention is a method to release from a precursor compound of formula (I), an aldehyde or a ketone of formula wherein the compound of formula (II) comprises at least 8 carbon atoms;

[0014] R1is a phenyl, a benzyl, a benzo[d][l,3]dioxole or a naphthyl group; with the phenyl and benzyl group being optionally substituted with one or more of a C1-8 alkyl, C1-8 alkoxy, hydroxy and / or C1-4 carboxylic ester group, or R1is a group of formula wherein the dashed line represents a single or a double bond; R3is a C2-12 hydrocarbon group optionally comprising one or two oxygen atoms; R4and R5, independently from each other, are a hydrogen atom or a C1-6 alkyl group; or R3and R4or R3and R5, when taken together, form a C5-15 cycloalkyl, C5-15 cycloalkenyl, C4-14 heterocycloalkyl or C4-14 heterocycloalkenyl group, each optionally substituted with one or more of a C1-15 hydrocarbon group, optionally comprising one or more oxygen atoms, wherein the heteroatom represents one or more oxygen atoms;

[0015] R2represents a hydrogen atom or a C1-15 hydrocarbon group;

[0016] R1and R2, when taken together, form a C5-15 cycloalkyl or C5-15 cycloalkenyl group wherein the double bond is not conjugated with the ketone functional group, a C4-14 heterocycloalkyl or C4-14 heterocycloalkenyl group wherein the double bond is not conjugated with the ketone functional group, each optionally substituted with one or more of a C1-15 alkyl, C1-15 alkoxy, C3-15 cycloalkyl, C5-15 cycloalkenyl, Ce-io aryl and / or Ce-io aryloxy group, each optionally substituted with one or more of a Ci-s alkyl, C1-8 alkoxy and / or C1-4 carboxylic ester group, wherein the heteroatom represents one or more oxygen atoms; wherein the precursor compound comprises a compound of formula in the form of any one of its stereoisomers or a mixture thereof, and wherein R1and R2have the same meaning as defined above; n is 1, 2, 3 or 4; X is an oxygen atom or a NR7group wherein R7is a hydrogen atom or a Ci-6 alkyl group; R6is a hydrogen atom, a sodium, potassium or ammonium cation or a Ci-i6 hydrocarbon group optionally containing one to nine oxygen atoms; by exposing the precursor compound of formula (I) to trace of water.

[0017] According to any one of the embodiments of the invention, the aldehyde or ketone of formula (II) is an active compound.

[0018] The terms “active compound”, “active volatile compound”, “active volatile aldehyde or ketone” or the similar, are understood as compounds being capable of bringing a benefit or effect into its surrounding environment. In particular, the “active compound” is selected from the group consisting of a perfuming ingredient, flavoring ingredient, malodor counteracting ingredient, antimicrobial ingredient and insect repellent or attractant ingredient. Therefore, to be considered as an “active compound” the compound has to possess at least one property which renders it useful as a perfuming ingredient, as a malodor counteracting ingredient, as a flavoring ingredient, as an antimicrobial ingredient and / or as an insect repellent or attractant.

[0019] The term “perfuming ingredient” is understood as a compound which is used as an active ingredient in perfuming preparations or compositions in order to impart a hedonic effect. In other words, a compound to be considered as being a perfuming ingredient, must be recognized by a skilled person in the art of perfumery as being able to impart or modify in a positive or pleasant way the odor of a composition, and not just as having an odor. The perfuming ingredient may impart an additional benefit beyond that of modifying or imparting an odor, such as long-lasting, blooming, malodor counteraction, antimicrobial effect, antiviral effect, microbial stability, or pest control. The term “flavoring ingredient” is understood as being capable of imparting a taste sensation to the taster’s pallet. The term “malodor counteracting ingredient” is understood as being capable of reducing the perception of malodor, i.e. of an odor that is unpleasant or offensive to the human nose. The term “antimicrobial ingredient” is understood as being capable of killing microorganisms or reducing or preventing their growth and / or accumulation and include antibacterial, antibiotic, antifungal, antiviral and antiparasitic ingredients. The term “insect attractant or repellent” is understood as a compound having a positive or negative effect on insects. Examples of insect attractant or repellent ingredients can be found in reference texts or in other works of a similar nature as for example: A. M. El-Sayed, 2024, The Pherobase: Database of Pheromones and Semiochemicals (https: / / www.pherobase.com).

[0020] According to the above and below mentioned embodiments of the invention, the method according to the present invention is particularly useful when the active compound is a perfuming ingredient, i.e. a perfuming aldehyde or ketone. A “perfuming aldehyde or ketone” is a perfuming ingredient as defined above comprising at least one ketone or aldehyde functional group. The perfuming aldehydes or ketones can be of natural or synthetic origin. Many of these perfuming aldehydes or ketones are in any case listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent versions, or in other works of a similar nature, as well as in the abundant patent literature in the field of perfumery.

[0021] Herein described, the terms “perfuming aldehyde or ketone” are also referred to as “perfuming compounds”.

[0022] Practically, the invention is carried out exactly in the same manner, independent of the exact properties of the active aldehyde or ketone. Therefore, it is understood that, even if the invention will be further illustrated herein below with a specific reference to “perfuming compounds”, the below embodiments are also applicable to other active aldehydes or ketones (i.e. it is possible to replace the expression “perfuming” with “flavoring”, “malodor counteracting”, “antibacterial”, “antimicrobial”, “insect attractant” or with “insect repellent” for instance).

[0023] The term “optionally” is understood that a certain group to be optionally substituted can or cannot be substituted with a certain functional group. The term “one or more” is understood as being substituted with 1 to 9, preferably 1 to 7, preferably 1 to 5, preferably 1 to 3 and more preferably 1 to 2 of a certain functional group.

[0024] Unless specified otherwise, all percentages refer to percent by weight, based on the total weight of the referenced composition.

[0025] The terms “alkyl” and “alkenyl” are understood as comprising branched and linear alkyl and alkenyl groups. The terms “alkenyl”, “cycloalkenyl” and “heterocycloalkenyl” are understood as comprising 1, 2 or 3 olefinic double bonds, preferably 1 or 2 olefinic double bonds, provided that the cycloalkenyl group is not an aryl group. The terms “cycloalkyl”, “cyclo alkenyl”, “heterocycloalkyl” and “heterocycloalkenyl” are understood as comprising a monocyclic or fused, spiro and / or bridged bicyclic or tricyclic cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl groups, preferably monocyclic cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl groups. The term “alkoxy” is understood as an -OR’ group wherein R’ is a linear branched or cyclic alkyl group. The term “Ci-4 carboxylic ester group” is understood as -OC(=O)R” or -C(=O)O-R” wherein R” is a linear branched or cyclic alkyl group.

[0026] The term “aryl” is understood as comprising any group comprising at least one aromatic group such as phenyl, indenyl, indanyl, benzodioxolyl, dihydrobenzodioxinyl, tetrahydronaphthalenyl or naphthalenyl group.

[0027] It is understood that by “... hydrocarbon group ...” it is meant that said group consists of hydrogen and carbon atoms and can be in the form of an aliphatic hydrocarbon, i.e. linear or branched saturated hydrocarbon (e.g. alkyl group), a linear or branched unsaturated hydrocarbon (e.g. alkenyl or alkynyl group), a saturated cyclic hydrocarbon (e.g. cycloalkyl) or an unsaturated cyclic hydrocarbon (e.g. cycloalkenyl or cycloalkynyl), or can be in the form of an aromatic hydrocarbon, i.e. aryl group, or can also be in the form of a mixture of said type of groups, e.g. a specific group may comprise a linear alkyl, a branched alkenyl (e.g. having one or more carbon-carbon double bonds), a (poly)cycloalkyl and an aryl moiety, unless a specific limitation to only one type is mentioned. Similarly, in all the embodiments of the invention, when a group is mentioned as being in the form of more than one type of topology (e.g. linear, cyclic or branched) and / or being saturated or unsaturated (e.g. alkyl, aromatic or alkenyl), it is also meant a group which may comprise moieties having any one of said topologies or being saturated or unsaturated, as explained above. Similarly, in all the embodiments of the invention, when a group is mentioned as being in the form of one type of saturation or unsaturation, (e.g. alkyl), it is meant that said group can be in any type of topology (e.g. linear, cyclic or branched) or having several moieties with various topologies.

[0028] It is understood that with the term “... a hydrocarbon group, optionally comprising one or more oxygen atoms... ” it is meant that said hydrocarbon group optionally comprises one, two, three or more oxygen atoms in a form of alcohol, ketone, aldehyde, ether, ester, carboxylic acid, carbonate groups. These groups can either substitute a hydrogen atom of the hydrocarbon group and thus be laterally attached to said hydrocarbon, or substitute a carbon atom (if chemically possible) of the hydrocarbon group and thus be inserted into the hydrocarbon chain. For example, a -CH2-CH2-CHOH-CH2- group represents a C4 hydrocarbon group comprising an alcohol group (substitution of a hydrogen atom), i.e. a C4 hydrocarbon comprising an oxygen atom; a -CH2-CH2-COO-CH2-CH2CH2-CH2- group represents a C7 hydrocarbon group comprising one ester group (substitution of carbon atoms / insertion into the hydrocarbon chain), i.e. a C7 hydrocarbon comprising two oxygen atoms and, similarly, a -CH2-CH2-O-CH2-CH2-O-CH2-CH2- group represents a Ce hydrocarbon group comprising two ether groups, i.e. a Ce hydrocarbon comprising two oxygen atoms.

[0029] For the sake of clarity, by the expression “any one of its stereoisomers or a mixture thereof’, or the similar, it is meant the normal meaning understood by a person skilled in the art, i.e. that the compound of formula (I) can be a pure enantiomer or diastereomer. In other words, the compound of formula (I) may possess several stereocenters and each of said stereocenter can have two different stereochemistries (e.g. R or S). The compound of formula (I) may even be in the form of a pure enantiomer or in the form of a mixture of enantiomers or diastereoisomers. The compound of formula (I) can be in a racemic form or scalemic form. Therefore, the compound of formula (I) can be one stereoisomer or in the form of a composition of matter comprising, or consisting of, various stereoisomers.

[0030] According to any one of the above embodiments of the invention, the compound of formula (I) is a C11-C70 compound, preferably a C12-C40 compound, even more preferably a C15-36 compound.

[0031] According to any one of the above embodiments of the invention, the compound of formula (II) comprises at least 9 carbon atoms, even at least 10 carbon atoms.

[0032] According to any one of the above embodiments of the invention, R6is a hydrogen atom, a sodium, potassium or ammonium cation or a C1-14 hydrocarbon group, optionally containing one to nine oxygen atoms. Particularly, R6is a hydrogen atom, a sodium, potassium or ammonium cation or a C1-12 hydrocarbon group, optionally containing one to nine oxygen atoms. Particularly, R6is a hydrogen atom, a sodium, potassium or ammonium cation or a C1-10 hydrocarbon group, optionally containing one to nine oxygen atoms. Particularly, R6is a hydrogen atom, a sodium, potassium or ammonium cation or a C1-10 hydrocarbon group, optionally containing one to six oxygen atoms. Particularly, when n is 1 then R6is hydrogen atom, a sodium, potassium or ammonium cation, a phenyl, benzyl, C1-10 alkyl, C2-10 alkenyl, C3-10 cycloalkyl or a C5-10 cyloalkenyl group or when n is 2, 3 or 4 then R6is a n valent C2-10 hydrocarbon group, optionally containing one to six oxygen atoms. Particularly, when n is 1 then R6is hydrogen atom, a sodium, potassium or ammonium cation, a phenyl, benzyl, Ci-s alkyl, C2-8 alkenyl, C3-8 cycloalkyl or a C5-8 cyloalkenyl group or when n is 2, 3 or 4 then R6is a n valent C2-8 hydrocarbon group, optionally containing one to six oxygen atoms. Particularly, when n is 1 then R6is hydrogen atom, a sodium, potassium or ammonium cation, a phenyl, benzyl, C1-6 alkyl, C2-6 alkenyl, C3-6 cycloalkyl or a C5-6 cyloalkenyl group or when n is 2, 3 or 4 then R6is a n valent C2-6 hydrocarbon group, optionally containing one to four oxygen atoms. Particularly, when n is 1 then R6is hydrogen atom, a sodium, potassium or ammonium cation, a phenyl, benzyl, C1-4 alkyl group. Particularly, R6is a hydrogen atom, a sodium cation or a C1-4 alkyl group. Particularly, R6is a hydrogen atom or a methyl, ethyl or tert-butyl group. Particularly, R6is a hydrogen atom or a methyl or ethyl group. Even more particularly, R6is a methyl or ethyl group.

[0033] According to any one of the above embodiments of the invention, n is 1 or 2. Particularly, n is 1.

[0034] According to any one of the above embodiments of the invention, R7is a hydrogen atom or a C1-5 alkyl group. Particularly, R7is a hydrogen atom or a C1-4 alkyl group. Particularly, R7is a hydrogen atom or a C1-3 alkyl group. Particularly, R7is a hydrogen atom or a C1-2 alkyl group. Even more particularly, R7is a hydrogen atom or a methyl group.

[0035] According to any one of the above embodiments of the invention, X is an oxygen atom.

[0036] According to any one of the above embodiments of the invention, the compound of formula (I) is a compound of formula in the form of any one of its stereoisomers or a mixture thereof, and wherein R1, R2and R6have the same meaning as defined above.

[0037] According to any one of the above embodiments of the invention, R1and R2are taken together and form a C5-14 cycloalkyl or C5-14 cycloalkenyl group wherein the double bond is not conjugated with the ketone functional group, a C4-12 heterocycloalkyl or C4-12 heterocycloalkenyl group wherein the double bond is not conjugated with the ketone functional group, each optionally substituted with one or more of a C1-15 alkyl, C1-15 alkoxy, C3-15 cycloalkyl, C5-15 cycloalkenyl, Ce-io aryl and / or Ce-io aryloxy group, each optionally substituted with one or more of a Ci-s alkyl, Ci-s alkoxy and / or C1-4 carboxylic ester group. Particularly, R1and R2are taken together and form a C5-12 cycloalkyl or C5-12 cycloalkenyl group wherein the double bond is not conjugated with the ketone or aldehyde functional group, each optionally substituted with one or more of a C1-15 alkyl, C1-15 alkoxy, C3-15 cycloalkyl, C5-15 cycloalkenyl, Ce-io aryl and / or Ce-io aryloxy group, each optionally substituted with one or more of a Ci-s alkyl, Ci-s alkoxy and / or C1-4 carboxylic ester group. Particularly, R1and R2are taken together and form a C5-12 cycloalkyl or a C5-12 cycloalkenyl group wherein the double bond is not conjugated with the ketone or aldehyde functional group, each optionally substituted with one or more of a C1-15 alkyl, C1-15 alkoxy, C3-15 cycloalkyl, C5-15 cycloalkenyl, Ce-io aryl and / or Ce-io aryloxy group, each optionally substituted with one or more of a C1-6 alkyl, C1-6 alkoxy and / or C1-4 carboxylic ester group. Particularly, R1and R2, are taken together and form a C5-12 cycloalkyl or C5-12 cycloalkenyl group wherein the double bond is not conjugated with the ketone or aldehyde functional group, each optionally substituted with one or more of a C1-12 alkyl, C1-12 alkoxy, C3-12 cycloalkyl, C5-12 cycloalkenyl, Ce aryl and / or Ce aryloxy group, each optionally substituted with one or more of a C1-6 alkyl, C1-6 alkoxy, carboxylic acid and / or C1-4 carboxylic ester group. Particularly, R1and R2, are taken together and form a C5-12 cycloalkyl or C5-12 cycloalkenyl group wherein the double bond is not conjugated with the ketone or aldehyde functional group, each optionally substituted with one or more of a C1-10 alkyl, C1-10 alkoxy, C3-10 cycloalkyl, C5-10 cycloalkenyl, Ce aryl and / or Ce aryloxy group, each optionally substituted with one or more of a C1-6 alkyl, C1-6 alkoxy, carboxylic acid and / or C1-4 carboxylic ester group. Particularly, R1and R2, are taken together and form a C5-12 cycloalkyl or C5-12 cycloalkenyl group wherein the double bond is not conjugated with the ketone or aldehyde functional group, each optionally substituted with one or more of a Ci-s alkyl, Ci-s alkoxy, C3-8 cycloalkyl, C5-8 cycloalkenyl, Ce aryl and / or Ce aryloxy group, each optionally substituted with one or more of a C1-6 alkyl, C1-6 alkoxy, carboxylic acid and / or C1-4 carboxylic ester group. Particularly, R1and R2, are taken together and form a C5-10 cycloalkyl or C5-10 cycloalkenyl group wherein the double bond is not conjugated with the ketone or aldehyde functional group, each optionally substituted with one or more of a C1-8 alkyl, C1-8 alkoxy, C3-8 cycloalkyl, C5-8 cycloalkenyl, Ce aryl and / or Ce aryloxy group, each optionally substituted with one or more of a C1-6 alkyl, C1-6 alkoxy, carboxylic acid and / or C1-4 carboxylic ester group. Particularly, R1and R2, are taken together and form a C5-8 cycloalkyl or C5-8 cycloalkenyl group wherein the double bond is not conjugated with the ketone or aldehyde functional group, each optionally substituted with one or more of a C1-8 alkyl, C1-8 alkoxy, C3-8 cycloalkyl, C5-8 cycloalkenyl, O, aryl and / or O, aryloxy group, each optionally substituted with one or more of a C1-6 alkyl, C1-6 alkoxy, carboxylic acid and / or C1-4 carboxylic ester group. Particularly, R1and R2, are taken together and form a C5-6 cycloalkyl or C5-6 cycloalkenyl group wherein the double bond is not conjugated with the ketone or aldehyde functional group, each optionally substituted with one or more of a C1-8 alkyl, C1-8 alkoxy, C3-8 cycloalkyl, C5-8 cycloalkenyl, Ce aryl and / or Ce aryloxy group, each optionally substituted with one or more of a C1-6 alkyl, C1-6 alkoxy, carboxylic acid and / or C1-4 carboxylic ester group. Particularly, R1and R2, are taken together and form a C5-6 cycloalkyl or C5-6 cycloalkenyl group wherein the double bond is not conjugated with the ketone or aldehyde functional group, each optionally substituted with one or more of a C1-6 alkyl, C1-6 alkoxy, C3-6 cycloalkyl, C5-6 cycloalkenyl, Ce aryl and / or Ce aryloxy group, each optionally substituted with one or more of a C1-4 alkyl, C1-4 alkoxy, carboxylic acid and / or C1-4 carboxylic ester group. Particularly, R1and R2, are taken together and form a C5-6 cycloalkyl or C5-6 cycloalkenyl group wherein the double bond is not conjugated with the ketone or aldehyde functional group, each optionally substituted with one or more of a C1-4 alkyl or C1-4 alkoxy group. Particularly, R1and R2, are taken together and form a C5-6 cycloalkyl or C5-6 cycloalkenyl group wherein the double bond is not conjugated with the ketone or aldehyde functional group, each optionally substituted with one or more of a C1-3 alkyl or C1-3 alkoxy group. Particularly, R1and R2, are taken together and form a C5-6 cycloalkyl group, optionally substituted with one or more of a C1-3 alkyl group.

[0038] Particularly, R1and R2are taken together and form a monocyclic cycloalkyl or heterocycloalkyl or a monocyclic cycloalkenyl or heterocycloalkenyl group wherein the double bond is not conjugated with the ketone functional group.

[0039] According to any one of the above embodiments of the invention, R2is a hydrogen atom or a C1-12 hydrocarbon group. Particularly, R2is a hydrogen atom or a C1-10 hydrocarbon group. Particularly, R2is a hydrogen atom or a C1-8 hydrocarbon group. Particularly, R2is a hydrogen atom or a C1-6 hydrocarbon group. Particularly, R2is a hydrogen atom or a C1-6 alkyl or C2-6 alkenyl group. Particularly, R2is a hydrogen atom or a C1-4 alkyl or C2-4 alkenyl group. Particularly, R2is a hydrogen atom or a C1-3 alkyl group. Particularly, R2is a hydrogen atom or a methyl or ethyl group. Even more particularly, R2is a hydrogen atom.

[0040] According to any one of the above embodiments of the invention, the compound of formula (I) is a compound of formula in the form of any one of its stereoisomers or a mixture thereof, and wherein R1and R6have the same meaning as defined above.

[0041] According to any one of the above embodiments of the invention, when R2is a hydrogen atom, then R1is not a 3-hydroxy-4-methoxyphenyl, a 4-hydroxy-3- methoxyphenyl, a benzyl, a phenyl or a 4-methoxyphenyl group.

[0042] According to any one of the above embodiments of the invention, R1is a phenyl, a benzyl, a benzo[d][l,3]dioxole or a naphthyl group; with the phenyl and benzyl group being optionally substituted with one or more of a Ci-6 alkyl, Ci-6 alkoxy, hydroxy and / or C1-3 carboxylic ester group, or R1is a group of formula (a). Particularly, R1is a phenyl or a benzyl group; each optionally substituted with one or more of a C1-4 alkyl, C1-4 alkoxy, hydroxy and / or C1-3 carboxylic ester group, or R1is a group of formula (a). Particularly, R1is a phenyl or a benzyl group; each optionally substituted with one or more of a C1-3 alkyl, C1-3 alkoxy, hydroxy and / or C1-3 carboxylic ester group, or R1is a group of formula (a). Particularly, R1is a phenyl or a benzyl group; each optionally substituted with one or more of a C1-2 alkyl, C1-2 alkoxy, hydroxy and / or C1-2 carboxylic ester group, or R1is a group of formula (a). Particularly, R1is a phenyl or a benzyl group; each optionally substituted with one or two of a methyl, methoxy, hydroxy and / or C1-2 carboxylic ester group, or R1is a group of formula (a). Particularly, R1is a group of formula (a). Even more particularly, R1comprises between 8 and 18 carbon atoms and is a group of formula (a).

[0043] According to any one of the above embodiments of the invention, R1comprises between 8 and 18 carbon atoms and is a group of formula (a). Particularly, R1comprises between 9 and 18 carbon atoms and is a group of formula (a). In other words, the compound of formula (I) is a compound of formula in the form of any one of its stereoisomers or a mixture thereof, and wherein R3, R4, R5and R6have the same meaning as defined above.

[0044] According to any one of the above embodiments of the invention, R3and R4or R3and R5, when taken together, form a C5-12 cycloalkyl, C5-12 cycloalkenyl, C4-12 heterocycloalkyl or C4-12 heterocycloalkenyl group, each optionally substituted with one or more of a C1-15 hydrocarbon, optionally comprising one or more oxygen atoms, wherein the heteroatom represents one or more oxygen atoms. Particularly, R3and R4or R3and R5, when taken together, form a C5-12 cycloalkyl, C5-12 cycloalkenyl, C4-12 heterocycloalkyl or C4-12 heterocycloalkenyl group, each optionally substituted with one or more of a C1-12 hydrocarbon, optionally comprising one or more oxygen atoms, wherein the heteroatom represents one or more oxygen atoms. Particularly, R3and R4or R3and R5, when taken together, form a C5-12 cycloalkyl, C5-12 cycloalkenyl, C4-12 heterocycloalkyl or C4-12 heterocycloalkenyl group, each optionally substituted with one or more of a C1-10 hydrocarbon, optionally comprising one or more oxygen atoms, wherein the heteroatom represents one or more oxygen atoms. Particularly, R3and R4or R3and R5, when taken together, form a C5-10 cycloalkyl, C5-10 cycloalkenyl, C4-10 heterocycloalkyl or C4-10 heterocycloalkenyl group, each optionally substituted with one or more of a C1-10 hydrocarbon, optionally comprising one or more oxygen atoms, wherein the heteroatom represents one or more oxygen atoms. Particularly, R3and R4or R3and R5, when taken together, form a C5-8 cycloalkyl, C5-8 cycloalkenyl, C4-8 heterocycloalkyl or C4-8 heterocycloalkenyl group, each optionally substituted with one or more of a C1-10 hydrocarbon, optionally comprising one or more oxygen atoms, wherein the heteroatom represents one or more oxygen atoms. Particularly, R3and R4or R3and R5, when taken together, form a C5-8 cycloalkyl, C5-8 cycloalkenyl, C4-8 heterocycloalkyl or C4-8 heterocycloalkenyl group, each optionally substituted with one or more of a C1-8 hydrocarbon, optionally comprising one or more oxygen atoms, wherein the heteroatom represents one or more oxygen atoms. Particularly, R3and R4or R3and R5, when taken together, form a C5-8 cycloalkyl, C5-8 cycloalkenyl, C4-8 heterocycloalkyl or C4-8 heterocycloalkenyl group, each optionally substituted with one or more of a C1-8 alkyl or C1-8 alkenyl group. Particularly, R3and R4or R3and R5, when taken together, form a C5-7 cycloalkyl or C5-7 cycloalkenyl, each optionally substituted with one or more of a C1-8 alkyl or C1-8 alkenyl group. Particularly, R3and R4or R3and R5, when taken together, form a C5-6 cycloalkyl or C5-6 cycloalkenyl, each optionally substituted with one or more of a C1-8 alkyl or Ci-8 alkenyl group. Particularly, R3and R4or R3and R5, when taken together, form a C5-6 cycloalkyl or C5-6 cycloalkenyl, each optionally substituted with one or more of a C1-6 alkyl or C1-6 alkenyl group. Particularly, R3and R4or R3and R5, when taken together, form a C5-6 cycloalkyl or C5-6 cycloalkenyl, each optionally substituted with one or more of a C1-4 alkyl or C1-4 alkenyl group. Particularly, R3and R4or R3and R5, when taken together, form a C5-6 cycloalkyl or C5-6 cycloalkenyl, each optionally substituted with one or more of a C1-3 alkyl or C1-3 alkenyl group. Even more praticularly, R3and R4or R3and R5, when taken together, form a C5-6 cycloalkyl or C5-6 cycloalkenyl, each optionally substituted with one or more of a methyl or ethyl group.

[0045] According to any one of the above embodiments of the invention, when R3and R5are taken together as defined above, then R4is a C1-6 alkyl group.

[0046] According to any one of the above embodiments of the invention, at least one group among R4and R5is not a hydrogen atom.

[0047] According to any one of the above embodiments of the invention, at least one group among R4and R5is a C1-6 alkyl group. Particularly, at least one group among R4and R5is a C1-4 alkyl group. Particularly, at least one group among R4and R5is a C1-3 alkyl group. Particularly, at least one group among R4and R5is a methyl or ethyl group. Even more particularly, at least one group among R4and R5is a methyl group.

[0048] According to any one of the above embodiments of the invention, R4is a hydrogen atom or a C1-4 alkyl group. Particularly, R4is a hydrogen atom or a C1-3 alkyl group. Particularly, R4is a hydrogen atom or a methyl or ethyl group. Even more particularly, R4is a hydrogen atom or a methyl group.

[0049] According to any one of the above embodiments of the invention, R5is a hydrogen atom or a C1-4 alkyl group. Particularly, R5is a hydrogen atom or a C1-3 alkyl group. Particularly, R5is a hydrogen atom or a methyl or ethyl group. Even more particularly, R5is a hydrogen atom or a methyl group.

[0050] According to any one of the above embodiments of the invention, R3is a C4-12 hydrocarbon group optionally comprising one or two oxygen atoms. Particularly, R3is a C4-10 hydrocarbon group optionally comprising one or two oxygen atoms. Particularly, R3is a C4-10 alkyl, alkenyl, arylalkyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkylalkenyl, cycloaleknylalkyl or cycloaleknylalkeyl group or a phenyl group; each optionally substituted by one or two hydroxy or C1-3 alkoxy groups or by one, two or three C1-4 alkyl groups. Particularly, R3is a C4-10 alkyl or alkenyl group or a C5-8 cycloalkyl or cycloalkenyl group; each optionally substituted by one or two hydroxy or C1-3 alkoxy groups or by one, two or three C1-4 alkyl groups; or R3is a a phenyl group; optionally substituted by one or two hydroxy or C1-3 alkoxy groups or by one, two or three C1-4 alkyl groups. Particularly, R3is a C4-10 alkyl or alkenyl group or a C5-7 cycloalkyl or cycloalkenyl group; each optionally substituted by one or two C1-4 alkyl groups; or R3is a a phenyl group; optionally substituted by one or two hydroxy or C1-3 alkoxy group or by one, two or three C1-4 alkyl groups. Particularly, R3is a C4-10 alkyl or alkenyl group or a C5-6 cycloalkyl or cycloalkenyl group; each optionally substituted by one or two C1-4 alkyl groups; or R3is a a phenyl group; optionally substituted by one or two hydroxy or C1-2 alkoxy group or by one C1-4 alkyl group. Particularly, R3is a C5-10 alkyl or alkenyl group or a C5-6 cycloalkyl or cycloalkenyl group; each optionally substituted by one or two C1-4 alkyl groups; or R3is a a phenyl group; optionally substituted by one or two hydroxy or C1-2 alkoxy group or by one C1-4 alkyl group. Even more particularly, R3is a C5-10 alkyl or alkenyl group or a Ce cycloalkyl or cycloalkenyl group; each optionally substituted by one or two C1-4 alkyl groups; or R3is a a phenyl group; optionally substitued by a methoxy or a C1-4 alkyl group.

[0051] According to a particular embodiment of the invention, the compound of formula (I) is a compound of formula in the form of any one of its stereoisomers or a mixture thereof, and wherein n, X and R6have the same meaning as defined above.

[0052] According to a particular embodiment of the invention, the compound of formula (I) is a compound of formula in the form of any one of its stereoisomers or a mixture thereof, and wherein n, X and R6have the same meaning as defined above.

[0053] According to a particular embodiment of the invention, the compound of formula (I) is a compound of formula (la) as defined herein.

[0054] According to any of the embodiments, the compounds of formula (I) are non-volatile and essentially odorless.

[0055] Non-volatile and essentially odorless compounds are advantageously characterized by a vapor pressure below 2.0 Pa, as obtained by calculation using the software EPIwin v. 3.10 (2000, available at the US Environmental Protection Agency). Preferably, said vapor pressure is below 0.2 Pa, or even more preferably below 0.02 Pa.

[0056] According to any of the embodiments, the compound of formula (II) is advantageously characterized by a vapor pressure between 200 and 0.1 Pa, as obtained by calculation using the software EPIwin v. 3.10 (2000, available at the US Environmental Protection Agency). According to another embodiment, said vapor pressure is preferably between 150 and 0.2 Pa, even more preferably between 100 and 0.3 Pa, most preferably between 47 and 0.4 Pa.

[0057] In a particular embodiment, the compound of formula (II) wherein R2is a hydrogen atom; i.e. aldehydes of formula R'CHO. may be selected from the group consisting of benzaldehyde, 3-(1.3-benzodioxol-5-yl)-2-methylpropanal. 3 -butoxybenzaldehyde, 5- cyclohexyl-2,4-dimethylpent-4-enal (Muguissimo®, origin: Firmenich SA, Geneva, Switzerland), decanal, 4,7-decadienal, 4-decenal, 8-decenal, 9-decenal, 3-(6,6-dimethyl- bicyclo[3, 1 , l]hept-2-en-2-yl)propanal, 2,4-dimethyl-3 -cyclohexene- 1 -carbaldehyde (Triplal®, origin: International Flavors & Fragrances, New York, USA), 3,5-dimethyl-3-cyclohexene-l- carbaldehyde, 3-(4.4-dimethylcyclohex-l-enyl)propanal (Tillenal®, origin: Firmenich SA, Geneva, Switzerland), 5,9-dimethyl-4,8-decadienal, 4,8-dimethyl-4,9-decadienal, 5,9- dimethyldec-4-enal, 3-(l,l- or 3,3-dimethyl-2,3-dihydro-lH-inden-4- or 5-yl)propanal (Hivemal® Neo, origin: Firmenich SA, Geneva, Switzerland). 2,6-dimethyl-5-heptenal (Melonal), 3 ,7 -dimethylo ctanal, 3 ,7 -dimethyl-6-octenal (Citronellal), (3,7-dimethyl-6- octenyl)acetaldehyde, 2-((3,7-dimethyloct-6-en-l-yl)oxy)acetaldehyde, dodecanal, 3- dodecenal, 4-dodecenal. 3-ethoxy-4-hydroxybenzaldehyde (Ethyl vanillin), 4-ethyl benzaldehyde, 2-hydroxybenzaldehyde, 9-hydroxy-5,9-dimethyl-4-decenal (Mahonial®, origin: Givaudan-Roure SA., Vernier, Switzerland), 7 -hydroxy-3 ,7 -dimethyloctanal (hydroxycitronellal), 4- and 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-l-carbaldehyde (Lyral®, origin: International Flavors and Fragrances, New York, USA), 3-(4-isobutyl-2- methylphenyl)propanal (Nympheal®, origin: Givaudan-Roure SA., Vernier, Switzerland), 3- (4-isobutylphenyl)propanal, 4-isopropylbenzaldehyde (Cuminaldehyde), 3-(4- isopropylcyclohex-l-en-l-yl)-2-methylpropanal, 3-(4-isopropylcyclohex-l -en-1 -yDpropanal, 8-isopropyl-6-methylbicyclo[2.2.2]oct-5-ene-2-carbaldehyde, 3-(3-isopropylphenyl)butanal (Florhydral®, origin: Givaudan-Roure SA., Vernier, Switzerland), 3-(4-isopropylphenyl)-2- methylpropanal (Cyclamen aldehyde), 2-(4-isopropylphenyl)propanal, 4- methoxybenzaldehyde (Anisaldehyde), 6-methoxy-2.6-dimethylheptanal (Methoxymelonal), 3-methoxy-4-hydroxybenzaldehyde (Vanillin), 3-(4-methoxyphenyl)-2-methylpropanal. 8(9)- methoxy-tricyclo[5.2.1.0.(2,6)]decane-3(4)-carbaldehyde (Scentenal®, origin: Firmenich SA, Geneva, Switzerland), 4-methylbenzaldehyde, 3 -(4-methyl-3 -cyclohexen- 1 -yDbutanal (Liminal®, origin: Firmenich SA, Geneva, Switzerland), 2-methyldecanal, 2-(4- methylenecyclohexyl)propanal, 4-methyl -5 -(4-methyl phenyl )pent-4-enal (Mimosal®, origin: Firmenich SA, Geneva, Switzerland), 3- and 4-(4-methyl-3-pentenyl)-3-cyclohexene-l- carbaldehyde (Empetal, origin: Givaudan-Roure SA., Vernier, Switzerland), (4- methylphenyl)acetaldehyde, 3 -methyl-5 -phenylpentanal (Phenexal®, origin: Firmenich SA, Geneva, Switzerland), 2-methyl-4-(2,2,3-trimethylcyclopent-3-en-l-yl)pent-4-enal, 2- methylundecanal, nonanal, 3-nonenal, 6-nonenal, 8-nonenal, 4-(octahydro-5H-4,7- methanoinden-5-ylidene)butanal, octanal, phenoxyacetaldehyde, phenylacetaldehyde, 3- phenylbutanal (Trifernal®, origin: Firmenich SA, Geneva, Switzerland), 2-phenylpropanal (Hydratropaldehyde), 3-phenylpropanaL 3-(4-tert-butylphenyl)-2-methylpropanal (Lilial®, origin: Givaudan-Roure SA, Vernier, Switzerland), 3-(4-tert-butylphenyl)propanal (Bourgeonal®, origin: Quest International, Naarden, Netherlands), tricyclo[5.2.1.0(2,6)]decane-4-carbaldehyde, exo-tricyclo[5.2.1.0(2,6)]decane-8exo- carbaldehyde (Vertral®, origin: Symrise, Holzminden, Germany), trideca-4,7-dienal, 2,6,6- trimethyl-bicyclo[3.1.1]heptane-3-carbaldehyde (Formyl pinane), 2,4,6- and 3,5,6-trimethyl- 3 -cyclohexene- 1 -carbaldehyde, 2,2,3-trimethyl-3-cyclopentene-l -acetaldehyde (Campholenic aldehyde), 6-(2,2,3-trimethylcyclo-3-pentenyl)-4-hexenal, 2,5, 6-trimethyl-4 -heptenal, 3,5,5- trimethylhexanal, 2,6, 10-trimethyl-9-undecenal, undecanal, 10-undecenal or 9-undecenal and their mixtures such as Intreleven aldehyde (origin: International Flavors & Fragrances, New York, USA) and Aldehyde Supra (origin: Firmenich SA, Geneva, Switzerland); wherein the underlined compounds represent, in a preferred embodiment of the invention, particularly useful aldehydes.

[0058] In a particular embodiment, the compound of formula (II) wherein R2is not a hydrogen atom; i.e. ketone of formula (R1)(R2)C=O, may be selected from the group consisting of 4-(1.3-benzodioxol-5-yl)-2-butanone. (4E7Z,8E7Z)-cyclododeca-4,8-dien-l-one, cyclopentadecanone, (Z)-cyclopentadec-4-en-l-one, (Z)-cycloheptadec-9-en-l-one, l-(3,5- diisopropylphenyl)ethan- 1 -one, 1 -(3,3 -dimethyl cyclohexyl)ethan- 1 -one, 1 -[2,6-dimethyl-4- (2-methyl-2-propanyl)phenyl]ethanone, 4,7-dimethyl-6-octen-3-one, 2,6-dimethyl-7-octen-4- one (Dihydrotagetone), 4-(l,l-dimethylpropyl)cyclohexan-l-one (Orivone®, origin: International Flavors & Fragrances, New York, USA), (5-E / Z)-6,10-dimethylundeca-5,9- dien-2-one, 2-ethyl-4,4-dimethylcyclohexan-l-one, 4-ethyl-8-methyloctahydronaphthalen- 1 (2H)-one, 1 -(4-ethylphenyl)ethan- 1 -one, 1 -(3 -ethyl- 1,1,3 ,6-tetramethyl-2,3 -dihydro- 1 H- inden-5-yl)ethanone, 2 -heptyl cyclopentan- 1 -one, 4,4a,6,7,8,8a-hexahydro-l,4- methanonaphthalen-5(lH)-one, 1 -(1,1, 2,3,3, 6-hexamethyl-2,3-dihydro-lH-inden-5- yl)ethanone (Phantolid®, origin: PFW Aroma Chemicals, Bamevald, The Netherlands), 1- (3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydro-2-naphthalenyl)ethan-l-one (Fixolide®, origin: Givaudan SA, Vernier, Switzerland), 2-(5 -hexen- 1 -yDcyclopentan- 1 -one, 4-(4- hydroxyphenyl)-2-butanone (Raspberry ketone), l-isopropyl-4-methylbicyclo[3.1.0]hexan-3- one, 5-isopropyl-2-methylcyclohexan-l-one, 2-isopropyl-5 -methyl cy cl ohexan- 1 -one

[0059] (Menthone), 1 -(5-isopropyl-2-methylcyclohex-2-en-l -yl)propan-l-one, 1 -(3-isopropyl- l,l,2,6-tetramethyl-5-indanyl)ethan-l-one, 4-(4-methoxyphenyl)-2-butanone. l-(4- methoxyphenyl)ethan-l-one (Acetanisole, origin: Givaudan SA, Vernier, Switzerland), l-(2- methoxyphenyl)propan-l-one, 7-methyl-2H-benzo[b][l,4]dioxepin-3(4H)-one, 2-(2-(4- methyl cyclohex-3 -en- 1 -yl)propyl)cyclopentan- 1 -one, 3 -methyl cyclopentadecan- 1 -one, 3 - methylcyclopentadec-4-en-l-one, 3-methylcyclopentadec-5-en-l-one, 5-methyl-3-heptanone, 6-methyl-5-hepten-2-one, 7-methyloctahydro-l,4-methanonaphthalen-6(2H)-one, methyl (Z)- 2-(3-oxo-2-(pent-2-en-l-yl)cyclopentyl)acetate (Methyl jasmonate), methyl 2-(3-oxo-2- pentylcyclopentyl)acetate (Hedione®, origin: Firmenich SA, Geneva, Switzerland), 3-methyl- 1-phenylbutan-l-one, l-(4-methylphenyl)ethan-l-one, 2-methyl-l-phenylpropan-l-one, l-(4- methylphenyl)propan- 1 -one, 1 - [4-(2-methyl-2-propanyl)phenyl] ethan- 1 -one, 2-( 1 - methylpropyl)cyclohexan-l-one, 2-nonanone, 4-nonanone, 1 -(octahydro-2, 3, 8, 8-tetramethyl-

[0060] 2 -naphthal enyl)-l -ethanone (isomeric mixture, Iso E Super®, origin: International Flavors &

[0061] Fragrances, New York, USA), 2-octanone, 3-octanone, 2-pentadecanone, 2- pentyl cyclopentan- 1 -one (Delphone, origin: Firmenich SA, Geneva, Switzerland), 1- phenylbutan-l-one, 4-phenyl-2-butanone, 1-phenylethan-l-one (Acetophenone), 1- phenylhexan-l-one, 1-phenylpentan-l-one, l-phenyl-4-penten-l-one (Lavonax, origin: International Flavors & Fragrances, New York, USA), 1-phenylpropan-l-one (Propiophenone), 7 -propyl-2H-benzo[b] [ 1 ,4]dioxepin-3 (4H)-one, 2-(tert-butyl)cyclohexan- 1 - one, 4-(tert-butyl)cyclohexan- 1 -one, 1 -(6-tert-butyl- 1 , 1 -dimethyl-4-indanyl)- 1 -ethanone (Crysolide, Givaudan SA, Vernier, Switzerland), 1 -(5,6,7, 8-tetrahydro-2-naphthal enyl)ethan- 1-one (Florantone®, origin: Takasago Corporation, Tokyo, Japan), 3, 6,8,8- tetramethylhexahydro-lH-3a,7-methanoazulen-5(4H)-one, l,l,5,5-tetramethylhexahydro-2H- 2,4a-methanonaphthalen-8(5H)-one (iso-Longifolanone), 2,4a,8,8- tetramethyloctahydrocyclopropa[d]naphthalen-3(lH)-one (Thujopsan-4-one), 2, 2, 7, 9- tetramethylspiro[5.5]undec-7-en-l -one, 2-tridecanone, 1 ,3,3-trimethylbicyclo[2.2. l]heptan-2- one, l,7,7-trimethylbicyclo[2.2.1]heptan-2-one, 2,2,4-trimethylbicyclo[3.1.1]heptan-3-one, 2,6,6-trimethylcycloheptan- 1 -one, 2,2,6-trimethylcyclohexan- 1 -one, 4-(2,6,6- trimethylcyclohex-2-en- 1 -yl)butan-2-one (Dihydro-alpha-ionone), 4-(2,6,6- trimethyl cyclohex- 1 -en- 1 -yl)butan-2-one (Dihydro-beta-ionone), 2,2,5-trimethyl-5- pentylcyclopentan-l-one, 2-undecanone and 5-undecanone; wherein the underlined compounds represent, in a preferred embodiment of the invention, particularly useful ketones.

[0062] According to any one of the above embodiments, the aldehyde or ketone of formula (II) is released from the precursor compound of formula (I) via hydrolysis; i.e. by exposing the precursor compound of formula (I) to a trace of water. For the sake of clarity, by the expression “trace of water”, or the like, it is meant the normal meaning understood by a person skilled in the art, i.e. small amounts of residual water on the target surface (cotton after the washing) as well as a minimum of humidity in the air, typically 20% of humidity, preferably 30%, even more preferably 50%, most preferably >60%. The hydrolysis occurs at room temperature, under air and atmospheric pressure and in the absence of a catalyst.

[0063] Without being bound by theory, it is also possible that, in addition to aqueous hydrolysis, the precursor compound of formula (I) can be hydrolyzed enzymatically to release the aldehyde or ketone of formula (II), e.g. by enzymes provided from bacteria, bacterial spores and / or other (micro-)organisms. Due to their natural occurrence, these enzymes might already be present on surfaces onto which the precursor has been deposited, or they might be intentionally brought to the target surface.

[0064] The present invention also relates to a microcapsule comprising at least one compound of formula (I). In one embodiment, the at least one compound of formula (I) is encapsulated in a core-shell microcapsule wherein the at least one compound of formula (I) is contained in the core surrounded by the shell. In one embodiment, the shell of the microcapsule protects the compound of formula (I) from the environment, e.g. from water. The shell is made of material which is able to release the at least one compound of formula (I) and / or the compound of formula (II). In one embodiment, the shell is made of material which is able to release the compound of formula (I) and / or the compound of formula (II) upon breakage of the shell and / or by diffusion through the shell. A person skilled in the art is well aware of processes to prepare said microcapsules. So, a microcapsule comprising at least one compound of formula (I) is one object of the present invention.

[0065] In a preferred embodiment, encapsulation of a compound of formula (I) may provide an environment within the capsule wherein all, or a portion of the compound of formula (I) may decompose, thereby releasing the individual aldehyde or ketone of formula (II) into the capsule. In a preferred embodiment, the shell of the microcapsule may act as a permeability barrier, preventing the leakage of the individual aldehyde or a ketone of formula (II) from the capsule.

[0066] According to a particular embodiment, the shell of the microcapsule comprises a material selected from the group consisting of polyurea, polyurethane, polyamide, polyester, poly(meth)acrylate (i.e. polyacrylate and / or polymethacrylate), polysiloxane, polycarbonate, polysulfonamide, polymers of urea and formaldehyde, melamine and formaldehyde, melamine and urea, or melamine and glyoxal and mixtures thereof. The shell can also be hybrid, namely organic-inorganic, such as a hybrid shell composed of at least two types of inorganic particles that are cross-linked, or yet a shell resulting from the hydrolysis and condensation reaction of a polyalkoxysilane macro -monomeric composition.

[0067] According to a particular embodiment, the core-shell microcapsule(s) can be also derived by using different or more than one encapsulation method.

[0068] In a preferred embodiment, the shell of the microcapsules may be, each independently, selected from the group of aminoplast, polyamide, polyester, polyurea and polyurethane shells and mixtures thereof.

[0069] In a particular embodiment, the shell of the microcapsules comprises an aminoplast copolymer, such as melamine-formaldehyde or urea-formaldehyde or cross-linked melamine formaldehyde or melamine glyoxal.

[0070] In a particular embodiment, the shell of the microcapsules is polyurea-based made from, for example, but not limited to isocyanate-based monomers and amine-containing crosslinkers, such as guanidine carbonate and / or guanazole. Certain polyurea microcapsules comprise a polyurea wall which is the reaction product of the polymerization between at least one polyisocyanate comprising at least two isocyanate functional groups and at least one reactant selected from the group consisting of an amine (for example a water-soluble guanidine salt and guanidine); a colloidal stabilizer or emulsifier; and an encapsulated perfume. However, the use of an amine can be omitted.

[0071] In a particular embodiment, the colloidal stabilizer includes an aqueous solution of between 0.1% and 0.4% of polyvinyl alcohol, between 0.6% and 1% of a cationic copolymer of vinylpyrrolidone and of a quatemized vinylimidazol (all percentages being defined by weight relative to the total weight of the colloidal stabilizer). In a particular embodiment, the emulsifier is an anionic or amphiphilic biopolymer, which may be for example chosen from the group consisting of Gum Arabic, soy protein, gelatin, sodium caseinate and mixtures thereof.

[0072] In a particular embodiment, the shell of the microcapsules is polyurethane-based made from, for example but not limited to polyisocyanate and polyols, polyamide, polyester, etc.

[0073] In a particular embodiment, the microcapsules have a polymeric shell resulting from complex coacervation wherein the shell is possibly cross-linked.

[0074] In a particular embodiment of the core-shell microcapsules, the core-shell microcapsules comprise an oil-based core comprising a hydrophobic active, preferably at least one compound of formula (I), and a composite shell comprising a first material and a second material, wherein the first material and the second material are different, the first material is a coacervate, the second material is a polymeric material.

[0075] In a particular embodiment, the weight ratio between the first material and the second material is comprised between 50:50 and 99.9:0.1.

[0076] In a particular embodiment, the coacervate comprises a first polyelectrolyte, preferably selected among proteins (such as gelatin), polypeptides or polysaccharides (such as chitosan), most preferably gelatin and a second polyelectrolyte, preferably alginate salts, cellulose derivatives, guar gum, pectinate salts, carrageenan, polyacrylic and methacrylic acid or xanthan gum, or yet plant gums such as acacia gum (Gum Arabic), most preferably Gum Arabic.

[0077] The first coacervate material can be hardened chemically using a suitable cross-linker such as glutaraldehyde, glyoxal, formaldehyde, tannic acid or genipin or can be hardened enzymatically using an enzyme such as transglutaminase.

[0078] The second polymeric material can be selected from the group consisting of polyurea, polyurethane, polyamide, polyester, polyacrylate, polysiloxane, polycarbonate, polysulfonamide, polymers of urea and formaldehyde, melamine and formaldehyde, melamine and urea, or melamine and glyoxal and mixtures thereof, preferably polyurea and / or polyurethane. The second material is preferably present in an amount less than 3% w / w, preferably less than 1% w / w based on the total weight of the microcapsule slurry.

[0079] The preparation of an aqueous dispersion / slurry of core-shell microcapsules is well known by a skilled person in the art. In a particular embodiment, the microcapsule wall material may comprise any suitable resin and especially including melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, etc. Suitable resins include the reaction product of an aldehyde and an amine, suitable aldehydes include formaldehyde and glyoxal. Suitable amines include melamine, urea, benzoguanamine, glycoluril, and mixtures thereof. Suitable melamines include methylol melamine, methylated methylol melamine, imino melamine and mixtures thereof. Suitable ureas include dimethylol urea, methylated dimethylol urea, urearesorcinol, and mixtures thereof. Suitable materials for making may be obtained from one or more of the following companies Solutia Inc. (St Louis, Missouri U.S.A.), Cytec Industries (West Paterson, New Jersey U.S.A.), Sigma-Aldrich (St. Louis, Missouri U.S.A.).

[0080] In a particular embodiment of the core-shell microcapsules, the core-shell microcapsule comprises an oil-based core comprising a hydrophobic active, preferably comprising at least one compound of formula (I), optionally an inner shell made of a polymerized polyfunctional monomer; a biopolymer shell comprising a protein, wherein at least one protein is crosslinked.

[0081] According to a particular embodiment, the protein is chosen from the group consisting of milk proteins, caseinate salts such as sodium caseinate or calcium caseinate, casein, whey protein, hydrolyzed proteins, gelatins, gluten, pea protein, soy protein, silk protein and mixtures thereof, preferably sodium caseinate.

[0082] According to a particular embodiment, the protein comprises sodium caseinate and a globular protein, preferably chosen from the group consisting of whey protein, betalactoglobulin, ovalbumine, bovine serum albumin, vegetable proteins, and mixtures thereof. The protein is preferably a mixture of sodium caseinate and whey protein.

[0083] According to a particular embodiment, the biopolymer shell comprises a crosslinked protein chosen from the group consisting of sodium caseinate and / or whey protein.

[0084] According to a particular embodiment, the microcapsule slurry comprises at least one microcapsule made of: an oil-based core comprising the hydrophobic active, preferably comprising at least one compound of formula (I); an inner shell made of a polymerized polyfunctional monomer; preferably a polyisocyanate having at least two isocyanate functional groups a biopolymer shell comprising a protein, wherein at least one protein is crosslinked; wherein the protein contains preferably a mixture comprising sodium caseinate and a globular protein, preferably whey protein. optionally at least an outer mineral layer.

[0085] According to an embodiment, sodium caseinate and / or whey protein is (are) crosslinked protein(s).

[0086] The weight ratio between sodium caseinate and whey protein is preferably comprised between 0.01 and 100, preferably between 0.1 and 10, more preferably between 0.2 and 5.

[0087] In a particular embodiment, the microcapsule is a one-shell aminoplast core-shell microcapsule obtainable by a process comprising the steps of:

[0088] 1) admixing a perfume oil with at least a polyisocyanate having at least two isocyanate functional groups to form an oil phase;

[0089] 2) dispersing or dissolving into water an aminoplast resin and optionally a stabilizer to form a water phase;

[0090] 3) preparing an oil-in-water dispersion, wherein the mean droplet size is comprised between 1 and 100 microns, by admixing the oil phase and the water phase;

[0091] 4) performing a curing step to form the wall of said microcapsule; and

[0092] 5) optionally drying the final dispersion to obtain the dried core-shell microcapsule.

[0093] In a particular embodiment, the core-shell microcapsule is a formaldehyde-free capsule. A typical process for the preparation of an aminoplast formaldehyde-free microcapsule slurry comprises the steps of

[0094] 1) preparing an oligomeric composition comprising the reaction product of, or obtainable by reacting together: a. a polyamine component in the form of melamine or of a mixture of melamine and at least one C1-C4 compound comprising two NH2 functional groups; b. an aldehyde component in the form of a mixture of glyoxal, a C4-6 2,2-dialkoxy-ethanal and optionally a glyoxalate, said mixture having a molar ratio glyoxal / C4-6 2,2-dialkoxy-ethanal comprised between 1 / 1 and 10 / 1; and c. a protic acid catalyst;

[0095] 2) preparing an oil-in-water dispersion, wherein the droplet size is comprised between 1 and 600 microns, and comprising: a. an oil; b. a water medium: c. at least an oligomeric composition as obtained in step 1; d. at least a cross-linker selected amongst: i. C4-C12 aromatic or aliphatic di- or tri-isocyanates and their biurets, triurets, trimmers, trimethylol propane-adduct and mixtures thereof; and / or ii. a di- or tri-oxiran compounds of formula:

[0096] Q-(oxiran-2-ylrnethyl)mwherein m stands for 2 or 3 and Q represents a C2-C6 group optionally comprising from 2 to 6 nitrogen and / or oxygen atoms; e. optionally a C1-C4 compound comprising two NH2 functional groups;

[0097] 3) heating the dispersion; and

[0098] 4) cooling the dispersion.

[0099] The above process is described in more detail in WO 2013 / 068255.

[0100] In a particular embodiment of the core-shell microcapsules, the core-shell microcapsule is a polyamide core-shell polyamide microcapsule comprising: an oil based core comprising an hydrophobic active, preferably comprising at least one compound of formula (I), and a polyamide shell comprising or being obtainable from:

[0101] • an acyl chloride, • a first amino compound, and

[0102] • a second amino compound.

[0103] According to a particular embodiment, the polyamide core-shell microcapsule comprises: an oil-based core comprising a hydrophobic active, preferably comprising at least one compound of formula (I), and a polyamide shell comprising or being obtainable from:

[0104] • an acyl chloride, preferably in an amount comprised between 5 and 98%, preferably between 20 and 98%, more preferably between 30 and 85% w / w,

[0105] • a first amino compound, preferably in an amount comprised between 1% and 50% w / w, preferably between 7 and 40% w / w;

[0106] • a second amino compound, preferably in an amount comprised between 1% and 50% w / w, preferably between 2 and 25% w / w,

[0107] • a stabilizer, preferably a biopolymer, preferably in an amount comprised between 0 and 90%, preferably between 0.1 and 75%, more preferably between 1 and 70%. According to a particular embodiment, the polyamide core-shell microcapsule comprises: an oil-based core comprising a hydrophobic active, preferably comprising at least one compound of formula (I), and a polyamide shell comprising or being obtainable from:

[0108] • an acyl chloride,

[0109] • a first amino-compound being an amino-acid, preferably chosen from the group consisting of L-Lysine, L-Arginine, L-Histidine, L-Tryptophane and / or mixture thereof.

[0110] • a second amino compound chosen from the group consisting of ethylene diamine, diethylene triamine, cystamine and / or mixture thereof, and

[0111] • a biopolymer chosen from the group consisting of casein, sodium caseinate, bovin serum albumin, whey protein, and / or mixture thereof.

[0112] The first amino-compound can be different from the second amino-compound.

[0113] Typically, a process for preparing a polyamide-based micrcoapsule includes the following steps: a) dissolving at least one acyl chloride in a hydrophobic material, preferably a perfume to form an oil phase; b) dispersing the oil phase obtained in step a) into a water phase comprising a first amino compound to form an oil-in water emulsion; c) performing a curing step to form polyamide microcapsules in the form of a slurry; wherein a stabilizer is added in the oil phase and / or in the water phase, and wherein at least a second amino-compound is added in the water phase before the formation of the oil-in-water emulsion and / or in the oil-in water emulsion obtained after step b).

[0114] In a particular embodiment, the shell of the microcapsule is polyurea-or polyurethane- based. Examples of processes for the preparation of polyurea and polyureathane-based microcapsule slurries are for instance described in WO 2007 / 004166, EP 2300146, and EP 2579976. Typically, a process for the preparation of polyurea or polyurethane-based microcapsule slurries includes the following steps: a) dissolving at least one polyisocyanate having at least two isocyanate groups in an oil to form an oil phase; b) preparing an aqueous solution of an emulsifier or colloidal stabilizer to form a water phase; c) adding the oil phase to the water phase to form an oil-in-water dispersion, wherein the mean droplet size is comprised between 1 and 500 pm, preferably between 5 and 50 pm; and d) applying conditions sufficient to induce interfacial polymerization and form microcapsules in form of a slurry.

[0115] In a particular embodiment, the microcapsules can be in form of a powder, which in particular may be obtained by submitting the microcapsule slurry to a drying step, like spraydrying, to provide the microcapsules as such, i.e. in a powdery form. It is understood that any standard method known by a person skilled in the art to perform such drying is also applicable. In particular, the slurry may be spray-dried, preferably in the presence of a polymeric carrier material such as polyvinyl acetate, polyvinyl alcohol, dextrins, natural or modified starch, gum Arabic, vegetable gums, pectins, xanthans, alginates, carrageenans or cellulose derivatives to provide microcapsules in a powder form.

[0116] However, one may also cite other drying methods such as extrusion, plating, spray granulation, the fluidized bed process, or even drying at room temperature using materials (carriers, desiccants) that meet specific criteria as disclosed in WO 2017 / 134179.

[0117] In another aspect, the present invention relates to a method to confer, enhance, improve or modify the odor properties of a perfuming composition, the air surrounding the perfuming composition, a surface or a perfumed article, comprising adding to the composition, the air, or article, or contacting or treating the surface with an effective amount of at least one compound of formula (I) as defined above. The term “surface”, as used herein may refer to a user’s skin, hair, a textile, or hard surface, on to which, a perfume composition comprising or containing the at least one compound of formula (I) is applied.

[0118] In another aspect, the present invention relates to a method for intensifying or prolonging the diffusion effect of the characteristic fragrance of an aldehyde or a ketone of formula (II) as defined above, on a surface or the air surrounding the perfuming composition, wherein the surface, or the air is treated with at least one compound (I) as defined above, or with a composition or article containing at least one compound (I), under conditions susceptible of allowing the release of a an aldehyde or a ketone of formula (II) over time.

[0119] Another object of the present invention is the use of the above-described compounds of formula (I) as delivery system to release perfuming compounds; i.e. use of a compound of formula (I) as defined above as perfuming ingredient to provide a long-lasting odor / effect. In other words, it concerns a method to confer, enhance, improve or modify the odor properties of a perfuming composition, the air surrounding the perfuming composition, a surface or a perfumed article, which method comprises adding to said composition, or article, or contacting or treating the surface with an effective amount of at least one compound of formula (I) as defined above. By “use of an invention’s compound” it has to be understood here also the use of any composition containing said compounds and which can be advantageously employed in perfumery industry as active ingredients.

[0120] The term “surface”, as used herein may refer to a user’s skin, hair, a textile, or hard surface, on to which, a perfume composition comprising or containing the at least one compound of formula (I) is applied.

[0121] For sake of clarity, a long-lasting effect is typically achieved if, after a certain time, e.g. after several hours or days, a given compound emits higher amounts of an odor into the environment than a reference compound. Whether a long-lasting odor effect is achieved can thus be verified by demonstrating that a given compound emits at a given time point higher headspace concentrations of a perfuming ingredient into the environment than an equimolar amount of the corresponding ingredient (reference), or by comparing the odor intensity that a given compound emits at a given time point with respect to a comparable amount of the reference in an olfactive panel evaluation. Said compositions, which in fact can be advantageously employed as perfuming ingredient, are also an object of the present invention.

[0122] Therefore, another object of the present invention is a perfuming composition comprising: i) as perfuming ingredient, at least one of the invention’s compounds of formula (I) as defined above; ii) at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base; and iii) optionally at least one perfumery adjuvant.

[0123] By “perfumery carrier” it is meant here a material which is practically neutral from a perfumery point of view, i.e. that does not significantly alter the organoleptic properties of perfuming ingredients. Said carrier may be a liquid or a solid.

[0124] As liquid carrier one may cite, as non-limiting examples, an emulsifying system, i.e. a solvent and a surfactant system, or a solvent commonly used in perfumery. A detailed description of the nature and type of solvents commonly used in perfumery cannot be exhaustive. However, one can cite as non-limiting examples, solvents such as butylene or propylene glycol, glycerol, dipropyleneglycol and its monoether, 1,2,3-propanetriyl triacetate, dimethyl glutarate, dimethyl adipate l,3-diacetyloxypropan-2-yl acetate, diethyl phthalate, isopropyl myristate, Abalyn® (rosin resins, available from Eastman), benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-l-ethano, tri-ethyl citrate or mixtures thereof, which are the most commonly used or also naturally derived solvents like glycerol or various vegetable oils such as palm oil, sunflower oil or linseed oil. For the compositions which comprise both a perfumery carrier and a perfumery base, other suitable perfumery carriers than those previously specified, can be also ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar (origin: Exxon Chemical) or glycol ethers and glycol ether esters such as those known under the trademark Dowanol (origin: Dow Chemical Company), or hydrogenated castor oils such as those known under the trademark Cremophor RH 40 (origin: BASF). Further suitable solvents include, but are not limited to, water-miscible solvents, such as diols. As understood by those of ordinary skill in the art, diols (also known as glycols) are compounds having two hydroxyl groups. Examples of diols include, but are not limited to, 1,2-alkanediols, such as ethylene glycol, 1,2- propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1 ,2-heptanediol, and 1,2- octanediol; 1,3-alkanediols, such as 1,3 -propanediol, 2-methyl-l,3-propanediol, and 3- methyl- 1,3 -butanediol; polyalkylene glycols, typically polyethylene glycols, polypropylene glycols, and poly(ethylene / propylene) glycols; and the like.

[0125] Solid carrier is meant to designate a material to which the perfuming composition or some element of the perfuming composition can be chemically or physically bound. In general, such solid carriers are employed either to stabilize the composition, or to control the rate of evaporation of the compositions or of some ingredients. Solid carriers are of current use in the art and a person skilled in the art knows how to reach the desired effect. However, by way of non-limiting example of solid carriers, one may cite absorbing gums or polymers or inorganic material, such as porous polymers, cyclodextrins, dextrins, maltodextrins, woodbased materials, organic or inorganic gels, clays, gypsum, talc or zeolites.

[0126] As other non-limiting examples of solid carriers, one may cite encapsulating materials. Examples of such materials may comprise wall-forming and plasticizing materials, such as glucose syrups, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetates, polyvinylalcohols, proteins or pectins, plant gums such as acacia gum (Gum Arabic), urea, sodium chloride, sodium sulfate, sodium carbonate, sodium bicarbonate, calcium carbonate, magnesium sulfate, calcium sulfate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, carbohydrates, saccharides such as sucrose, mono-, di-, tri- and polysaccharides and derivatives such as chitosan, starch, cellulose, carboxymethyl methylcellulose, methylcellulose, hydroxyethyl cellulose, ethyl cellulose, propyl cellulose, polyols / sugar alcohols such as sorbitol, maltitol, xylitol, erythritol and isomalt, polyethylene glycol (PEG), polyvinyl pyrrolidin (PVP), polyvinyl alcohol, acrylamides, acrylates, polyacrylic acid and related structures, maleic anhydride copolymers, amine-functional polymers, vinyl ethers, styrenes, polystyrenesulfonates, vinyl acids, ethylene glycol-propylene glycol block copolymers, pectins, xanthanes, alginates, carragenans, citric acid or any water soluble solid acid, fatty alcohols or fatty acids and mixtures thereof, or yet the materials cited in reference texts such as H. Scherz, Hydrokolloide: Stabilisatoren, Dickungs- und Geliermittel in Lebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitat, Behr's Verlag GmbH & Co., Hamburg, 1996. The encapsulation is a well-known process to a person skilled in the art, and may be performed, for instance, by using techniques such as spraydrying, agglomeration or yet extrusion; or consists of a coating encapsulation, including coacervation and complex coacervation techniques.

[0127] As non-limiting examples of solid carriers, one may cite in particular the core-shell capsules with resins of aminoplast, polyamide, polyester, polyurea or polyurethane type or a mixture thereof (all of said resins are well known to a person skilled in the art) using techniques like phase separation process induced by polymerization, interfacial polymerization, coacervation or altogether (all of said techniques have been described in the prior art), optionally in the presence of a polymeric stabilizer or of a cationic copolymer.

[0128] Resins may be produced by the polycondensation of an aldehyde (e.g. formaldehyde, 2,2-dimethoxyethanal, glyoxal, glyoxylic acid or glycolaldehyde and mixtures thereof) with an amine such as urea, benzoguanamine, glycouryl, melamine, methylol melamine, methylated methylol melamine, guanazole and the like, as well as mixtures thereof. Alternatively, one may use preformed resins alkylolated polyamines such as those commercially available under the trademark Urac® (origin: Cytec Technology Corp.), Cymel® (origin: Cytec Technology Corp.), Urecoll® or Luracoll® (origin: BASF).

[0129] Other resins are those produced by the polycondensation of an a polyol, like glycerol, and a polyisocyanate, like a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate or xylene diisocyanate or a Biuret of hexamethylene diisocyanate or a trimer of xylene diisocyanate with trimethylolpropane (known with the tradename of Takenate®, origin: Mitsui Chemicals), among which a trimer of xylene diisocyanate with trimethylolpropane and a Biuret of hexamethylene diisocyanate are preferred.

[0130] Some of the seminal literature related to the encapsulation of perfumes by polycondensation of amino resins, namely melamine-based resins with aldehydes includes articles such as those published by K. Dietrich et al. Acta Polymerica, 1989, Vol. 40, pages 243, 325 and 683, as well as 1990, Vol. 41, page 91. Such articles already describe the various parameters affecting the preparation of such core-shell microcapsules following prior art methods that are also further detailed and exemplified in the patent literature. US 4'396'670, to the Wiggins Teape Group Limited, is a pertinent early example of the latter. Since then, many other authors have enriched the literature in this field and it would be impossible to cover all published developments here, but the general knowledge in encapsulation technology is very significant. More recent publications of pertinence, which disclose suitable uses of such microcapsules, are represented for example by the article of K. Bruyninckx and M. Dusselier, ACS Sustainable Chemistry & Engineering, 2019, Vol. 7, pages 8041-8054.

[0131] By “perfumery base” what is meant here is a composition comprising at least one perfuming co-ingredient. The perfuming co-ingredient is not a compound according to the invention. Moreover, by the term “perfuming co-ingredient” is meant a perfuming ingredient as defined above.

[0132] The nature and type of the perfuming co -ingredients present in the base do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of general knowledge and according to intended use or application and the desired organoleptic effect. In general terms, these perfuming coingredients belong to chemical classes as varied as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, thiols, terpene hydrocarbons, nitrogenous or sulfurous heterocyclic compounds and essential oils, and the perfuming co-ingredients can be of natural or synthetic origin. In particular, one may cite perfuming co-ingredients which are commonly used in perfume formulations, such as:

[0133] Aldehydic ingredients: decanal, dodecanal, 2-methylundecanal, 10-undecenal, octanal, nonanal and / or nonenal;

[0134] Aromatic-herbal ingredients: eucalyptus oil, camphor, eucalyptol, 5- methyltricyclo[6.2.1.02,7]undecan-4-one, 1 -methoxy-3 -hexanethiol, 2-ethyl-4,4- dimethyl-l,3-oxathiane, 2,2,7 / 8,9 / 10-tetramethylspiro[5.5]undec-8-en-l-one, menthol and / or alpha-pinene;

[0135] Balsamic ingredients: ethyl vanillin and / or vanillin;

[0136] Citrus ingredients: dihydro myrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpenes, limonene, l-p-menthen-8-yl acetate and / or l,4(8)-p-menthadiene;

[0137] Floral ingredients: methyl dihydrojasmonate, linalool, citronellol, phenylethanol, 3-(4- tert-butylphenyl)-2-methylpropanal, benzyl acetate, benzyl salicylate, tetrahydro-2- isobutyl-4-methyl-4(2H)-pyranol, beta ionone, (E)-3-methyl-4-(2,6,6-trimethyl-2- cyclohexen-l-yl)-3-buten-2-one, (lE)-l-(2,6,6-trimethyl-2-cyclohexen-l -yl)-I -penten- 3-one, (2E)-l-(2,6,6-trimethyl-2-cyclohexen-l -yl)-2-buten-l-one, (2 / / )- 1 -| 2.6.6- trimethyl-3 -cyclohexen- 1 -yl] -2-buten- 1 -one, (2 / / )- 1 -(2,6,6-trimethyl- 1 -cyclohexen- 1 - yl)-2-buten-l-one, 2,5-dimethyl-2-indanmethanol, 2,6,6-trimethyl-3-cyclohexene-l- carboxylate, 3 -(4,4 -dimethyl- 1 -cyclohexen- l-yl)propanal, hexyl salicylate, 3,7- dimethyl-l,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, verdyl acetate, geraniol, p-menth-l-en-8-ol, 4-(l,l -dimethyl ethyl)- 1 -cyclohexyl e acetate, 1,1 -dimethyl - 2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate , high cis methyl dihydrojasmonate, 3 -methyl-5 -phenyl- 1 -pentanol, verdyl propri onate, geranyl acetate, tetrahydro linalool, cis-7-p-menthanol, propyl (S)-2-( 1 , 1 - dimethylpropoxy)propanoate, 2, 2, 2-trichloro-l -phenylethyl acetate, 4 / 3-(4-hydroxy-4- methylpentyl)-3 -cyclohexene- 1 -carbaldehyde, 8-decen-5-olide, 4-phenyl-2-butanone, isononyle acetate, 4-(l,l -dimethyl ethyl)- 1 -cyclohexyl acetate, verdyl isobutyrate and / or mixture of methylionone isomers;

[0138] Fruity ingredients: gamma-undecal actone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2- methyl-4-propyl-l,3-oxathiane, 4-decanolide, ethyl 2-methyl-pentanoate, hexyl acetate, ethyl 2-methylbutanoate, gamma-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-l,3-dioxolane-2-acetate, 3-(3,3 / l,l-dimethyl-5- indanyl)propanal, diethyl 1,4-cyclohexanedicarboxylate, 3-methyl-2-hexen-l-yl acetate, oct-2-en-4-one, 4-(4-hydroxyphenyl)-2-butanone, l-[3,3-dimethylcyclohexyl]ethyl [3- ethyl-2-oxiranyl] acetate and / or diethyl 1 ,4-cyclohexane dicarboxylate;

[0139] Green ingredients: 2-methyl-3 -hexanone (7 / )-oxime. 2,4-dimethyl-3-cyclohexene-l- carbaldehyde, 2 -tert-butyl- 1 -cyclohexyl acetate, styrallyl acetate, allyl (2- methylbutoxy)acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z)-3-hexen-l-ol and / or 1 -(5, 5 -dimethyl- 1 -cyclohexen-1 -yl)-4-penten-l -one;

[0140] Musk ingredients: l,4-dioxa-5,17-cycloheptadecanedione, (Z)-4-cyclopentadecen-l- one, 3-methylcyclopentadecanone, l-oxa-12-cyclohexadecen-2-one, l-oxa-13- cyclohexadecen-2-one, (9Z)-9-cycloheptadecen-l-one, 2-{15)-l-[(17?)-3,3- dimethyl cyclohexyl] ethoxy} -2-oxoethyl propionate 3 -methyl-5 -cyclopentadecen- 1 -one, 4,6,6,7,8,8-hexamethyl-l,3,4,6,7,8-hexahydrocyclopenta[g]isochromene, (15, 17?)-2-[l - (3',3'-dimethyl-l'-cyclohexyl)ethoxy]-2-methylpropyl propanoate, oxacyclohexadecan- 2-oneand / or ( 1 .17?)-| I -(3'.3'-dimethyl- 1 '-cyclohexyl)ethoxycarbonyl]methyl propanoate;

[0141] Woody ingredients: I -|( I / ?5.65 / ?)-2.2.6-trimethyl cyclohexyl |-3-hexanol. 3,3-dimethyl- 5-|(IA’)-2.2.3-trimethyl-3-cyclopenten- l -yl |-4-penten-2-ol. 3,4'-dimethylspiro[oxirane- 2,9'-tricyclo[6.2.1.02,7]undec[4]ene, (l-ethoxyethoxy)cyclododecane, 2,2,9,11- tetramethylspiro[5.5]undec-8-en-l -yl acetate, l-(octahydro-2,3,8,8-tetramethyl-2- naphtalenyl)-! -ethanone, patchouli oil, terpenes fractions of patchouli oil, Clearwood®, (1 ?,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-r-yl)-2-buten-l-ol, 2-ethyl-4-(2,2,3- trimethyl-3-cyclopenten-l-yl)-2-buten-l-ol, methyl cedryl ketone, 5-(2,2,3-trimethyl-3- cyclopentenyl)-3-methylpentan-2-ol, l-(2,3,8,8-tetramethyl-l,2,3,4,6,7,8,8a- octahydronaphthalen-2-yl)ethan-l-one and / or isobomyl acetate;

[0142] Other ingredients (e.g. amber, powdery spicy or watery): dodecahydro-3a,6,6,9a- tetramethyl-naphtho[2,l-b]furan and any of its stereoisomers, heliotropin, anisic aldehyde, eugenol, cinnamic aldehyde, clove oil, 3-(l,3-benzodioxol-5-yl)-2- methylpropanal, 7-methyl-2H-l,5-benzodioxepin-3(4H)-one, 2,5,5-trimethyl- l,2,3,4,4a,5,6,7-octahydro-2-naphthalenol, 1-phenylvinyl acetate, 6-methyl-7-oxa-l- thia-4-azaspiro[4.4]nonan and / or 3-(3-isopropyl-l-phenyl)butanal.

[0143] A composition according to the invention may not be limited to the above-mentioned perfuming co-ingredients, and many other of these co -ingredients are in any case listed in reference texts such as the book by S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its more recent versions, or in other works of a similar nature, as well as in the abundant patent literature in the field of perfumery. It is also understood that said co-ingredients may also be compounds known to release in a controlled manner various types of perfuming ingredients also known as properfumes or profragrances. Non-limiting examples of suitable properfumes may include 4-(dodecylthio)-4-(2,6,6- trimethyl-2-cyclohexen- 1 -yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl- 1 -cyclohexen- 1 - yl)-2-butanone, 3-(dodecylthio)-l-(2,6,6-trimethyl-3-cyclohexen-l-yl)-l-butanone, 3- (dodecylsulfonyl)-l-(2,6,6-trimethylcyclohex-3-en-l-yl)butan-l-one, a linear polysiloxane co-polymer of (3-mercaptopropyl)(methyl)dimethoxysilane, 3-(dodecylthio)-l-(6-ethyl-2,6- dimethyl cyclohex-3 -en- 1 -yl)butan- 1 -one, 2-(dodecylthio)octan-4-one, 2-

[0144] (dodecylsulfonyl)octan-4-one, 4-oxooctan-2-yl dodecanoate, 2-phenylethyl oxo (phenyl) acetate, 3,7-dimethylocta-2,6-dien-l-yl oxo (phenyl) acetate, (Z)-hex-3-en-l-yl oxo (phenyl) acetate, 3,7-dimethyl-2,6-octadien-l-yl hexadecanoate, bis(3,7-dimethylocta-2,6- dien-l-yl) succinate, 2E,6Z)- nona-2,6-dien-l-yl tetradecanoate, (2 / / .6Z)-nona-2.6-dien- l -yl dodecanoate, (2 / / .6Z)-nona-2.6-dien- 1 -yl hexadecanoate, (2-((2-methylundec-l-en-l- yl)oxy)ethyl)benzene, 1 -methoxy-4-(3-methyl-4-phenethoxybut-3 -en- 1 -yl)benzene, (3 - methyl-4-phenethoxybut-3-en-l-yl)benzene, l-(((Z)-hex-3-en-l-yl)oxy)-2-methylundec-l- ene, (2-((2-methylundec-l-en-l-yl)oxy)ethoxy)benzene, 2-methyl-l-(octan-3-yloxy)undec-l- ene, 1 -methoxy-4-(l -phenethoxyprop- 1 -en-2-yl)benzene, 1 -methyl-4-(l -phenethoxyprop- 1 - en-2-yl)benzene, (2-phenethoxyvinyl)benzene, (2-((2- pentylcyclopentylidene)methoxy)ethyl)benzene, 4-allyl-2-methoxy- 1 -((2-methoxy-2- phenylvinyl)oxy)benzene, (2-((2 -heptyl cyclopentylidene)methoxy)ethyl)benzene, 1 -methoxy- 4-(l -phenethoxyprop- 1 -en-2-yl)benzene, (2-((2-methyl-4-(2, 6, 6-trimethyl cyclohex- 1-en-l- yl)but-l -en-l-yl)oxy)ethyl)benzene, 1 -methoxy-4-(2-methyl-3-phenethoxyallyl)benzene, (2- ((2-isopropyl-5-methylcyclohexylidene)methoxy)ethyl)benzene, 1 -isopropyl-4-methyl-2-((2- pentyl cyclopentylidene)methoxy)benzene, 2-methoxy- 1 -((2- pentylcyclopentylidene)methoxy)-4-propylbenzene, 3-methoxy-4-((2-methoxy-2- phenylvinyl)oxy)benzaldehyde, l-isopropyl-2-((2-methoxy-2-phenylvinyl)oxy)-4- methylbenzene, 4-((2-(hexyloxy)-2-phenylvinyl)oxy)-3-methoxybenzaldehyde, 3-methyl-5- phenylpentyl hexadecanoate, 3 -(dodecyl thio)-2-methyl-l -(2,6,6-trimethylcyclohex-3-en-l - yl)butan-l-one, 3,5-bis(l-(4-isopropylphenyl)propan-2-yl)dihydro-lH,3H,5H-oxazolo[3,4- c]oxazole, 3,5-di(undecan-2-yl)dihydro-lH,3H,5H-oxazolo[3,4-c]oxazole, 3,5-bis(2,4- dimethylcyclohex-3-en-l-yl)dihydro-lH,3H,5H-oxazolo[3,4-c]oxazole, ethyl 2-acetyl-4- methyltridec-2-enoate, dec-9-en-l-yl (E)-3-(2-hydroxyphenyl)acrylate, 4-(dodecylthio)-4- methylpentan-2-one, methyl or ethyl N,S-bis(4-oxo-4-(2,6,6-trimethylcyclohex-3-en-l- yl)butan-2-yl)-L-cysteinate, 1 -butoxy-3-((lE',4Z)-hepta-l,4-dien-l -yl)benzene, 2-methoxy-4- ((lE,4Z)-hepta-l,4-dien-l-yl)phenol, 2-ethoxy-4-((l / / .4Z)-hepta-l .4-dien- l -yl)phenol, 1- methoxy-4-(3-phenylprop-l-en-l-yl)benzene or a mixture thereof.

[0145] In a particular embodiment, the perfuming composition according to the invention comprises a perfumery adjuvant.

[0146] The term “perfumery adjuvant” is understood as an ingredient capable of imparting additional added benefit such as a color, a particular light resistance, chemical stability and etc. A detailed description of the nature and type of adjuvant commonly used in perfuming bases cannot be exhaustive, but it has to be mentioned that the ingredients are well known to a person skilled in the art. However, one may cite as specific non-limiting examples the following: viscosity agents (e.g. surfactants, thickeners, gelling and / or rheology modifiers), stabilizing agents (e.g. preservatives, antioxidants, heat / light and or buffers or chelating agents, such as BHT), coloring agents (e.g. dyes and / or pigments), preservatives (e.g. antibacterial or antimicrobial or antifungal or anti-irritant agents), abrasives, skin cooling agents, fixatives, insect repellants, ointments, vitamins and mixture thereof. By “fixative” also called “modulator”, it is understood here an agent having the capacity to affect the manner in which the odor, and in particular the evaporation rate and intensity, of the compositions incorporating said modulator can be perceived by an observer or user thereof, over time, as compared to the same perception in the absence of the modulator. In particular, the modulator allows prolonging the time during which their fragrance is perceived. Non-limiting examples of suitable modulators may include methyl glucoside polyol; ethyl glucoside polyol; propyl glucoside polyol; isocetyl alcohol; PPG-3 myristyl ether; neopentyl glycol diethylhexanoate; sucrose laurate; sucrose dilaurate, sucrose myristate, sucrose palmitate, sucrose stearate, sucrose distearate, sucrose tristearate, hyaluronic acid disaccharide sodium salt, sodium hyaluronate, propylene glycol propyl ether; di cetyl ether; polyglycerin-4 ethers; isoceteth-5; isoceteth-7, isoceteth-10; isoceteth-12; isoceteth-15; isoceteth-20; isoceteth-25; isoceteth-30; disodium lauroamphodipropionate; hexaethylene glycol monododecyl ether; and their mixtures; neopentyl glycol diisononanoate; cetearyl ethylhexanoate; panthenol ethyl ether, DL-panthenol, n-hexadecyl n-nonanoate, noctadecyl n-nonanoate, cyclodextrin, and a combination thereof. At most 20% by weight, based on the total weight of the perfuming composition, of the modulator may be incorporated into the perfumed consumer product.

[0147] It is understood that a person skilled in the art is perfectly able to design optimal formulations for the desired effect by admixing the above-mentioned components of a perfuming composition, simply by applying the standard knowledge of the art as well as by trial-and-error methodologies.

[0148] Other suitable perfumery adjuvants optionally used in combination with the compounds according to the present invention comprise tertiary amines, in particular those with high water solubility, such as triethanolamine, methyldiethanolamine, dimethylethanolamine, alkyldiethanolamines and ethoxylated alkyldiethanolamines.

[0149] According to a particular embodiment of the invention, said tertiary amines are present in the compositions of the invention at a weight concentration of 0.0% to 10%, relative to the total weight of the composition. According to more preferred embodiments of the invention, the concentration of tertiary amines is comprised between 0.001 and 5% of the total weight, preferably between 0.005 and 0.5%.

[0150] A particular aspect of the invention’s perfumery compositions concerns those further comprising (in addition to the above mentioned compositions) at least one compound selected amongst the isothiazolones of formula wherein

[0151] Raand Rbrepresent, separately and independently of each other, a hydrogen atom, a halogen atom, preferably chlorine, a C1-C4 linear or branched alkyl group, an amino group or a benzylamino group; or, alternatively, Raand Rbare taken together to represent a phenyl or pyridine ring, possibly substituted with one to four C1-C4 linear or branched alkyl or alkenyl groups and / or one to two halogen atoms, preferably chlorine atoms; and

[0152] Rcrepresents a hydrogen atom, an alkali metal atom, in particular Na or K, a phenyl or benzyl group possibly substituted with one or two halogen atoms and / or one or two methyl, trifluoromethyl, methoxy or amino groups, an amine group, or a Ci-Cs unsaturated, linear, branched or cyclic hydrocarbon group possibly substituted with one or two nitrogen, oxygen or halogen atoms.

[0153] According to a particular embodiment of the invention, said compound of formula (V) is one wherein Raand Rbrepresent, separately and independently of each other, a hydrogen atom, a chlorine atom or a methyl group or, alternatively, Raand Rbare taken together to represent a phenyl ring, and Rcrepresents a hydrogen atom or a methyl group.

[0154] According to a particular embodiment of the invention, said compound of formula (V) is selected from the group of isothiazolones consisting of l,2-benzisothiazol-3(277)-one (as e.g. commercialized under the tradename Proxel® GXL), 4- or 5-chloro-2-methylisothiazol- 3(277)-one and 2-methylisothiazol-3(277)-one. In an embodiment, the compound of formula (V) is 5-chloro-2-methylisothiazol-3(2 / / )-one or l,2-benzisothiazol-3(277)-one, typically 1,2- benzisothiazol-3(277)-one.

[0155] According to a particular embodiment of the invention, said compound of formula (V) is present in the compositions of the invention at a weight concentration of 0.0% to 5%, relative to the total weight of the composition. According to more preferred embodiments of the invention, the concentration of compound of formula (V) is comprised between 0.001 and 3% of the total weight, preferably between 0.005 and 0.1%.

[0156] An invention’s composition consisting of at least one compound of formula (I) and at least one perfumery carrier consists of a particular embodiment of the invention as well as a perfuming composition comprising at least one compound of formula (I), at least one perfumery carrier, at least one perfumery base, and optionally at least one perfumery adjuvant.

[0157] According to a particular embodiment, the compositions mentioned above, comprise more than one compound of formula (I) and enable the perfumer to prepare accords or perfumes possessing the odor tonality of various compounds of the invention, creating thus new building block for creation purposes.

[0158] For the sake of clarity, it is also understood that any mixture resulting directly from a chemical synthesis, e.g. a reaction medium without an adequate purification, in which the compound of the invention would be involved as a starting, intermediate or end-product could not be considered as a perfuming composition according to the invention as far as said mixture does not provide the inventive compound in a suitable form for perfumery. Thus, unpurified reaction mixtures are generally excluded from the present invention unless otherwise specified.

[0159] The invention’s compound can also be advantageously used in all the fields of modem perfumery, i.e. fine or functional perfumery, to positively impart or modify the odor of a consumer product into which said compound (I) is added. Consequently, another object of the present invention consists of a perfumed consumer product comprising, as a perfuming ingredient, at least one compound of formula (I), as defined above.

[0160] The invention’s compound can be added as such or as part of an invention’s perfuming composition.

[0161] For the sake of clarity, it has to be mentioned that the term “perfumed consumer product” is understood as a consumer product, which is expected to deliver at least a pleasant perfuming effect to the surface to which it is applied (e.g. skin, hair, textile, or hard surface). In other words, a perfumed consumer product according to the invention is a perfumed consumer product, which comprises the inventive compound or perfuming composition, as well as optionally additional benefit agents, corresponding to the desired consumer product, e.g. a conditioner, a detergent or an air freshener, and an olfactorily effective amount of the perfuming composition according to the invention. For the sake of clarity, the perfuming consumer product is a non-edible product.

[0162] The nature and type of the constituents of the perfuming consumer product do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to the nature and the desired effect of the product.

[0163] In a particular embodiment, the perfumed consumer product is a perfume, a fabric care product, a body-care product, a cosmetic preparation, a skin-care product, an air care product or a home care product.

[0164] Non-limiting examples of suitable perfumed consumer products include a perfume, such as a fine perfume, a splash or an eau de parfum, a cologne or a shave or after-shave lotion; a fabric care product, such as a liquid or solid detergent optionally in the form of a dissolvable tile, dissolvable laundry sheet, a pod or tablet, a fabric softener, a liquid or solid scent booster, a dryer sheet, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtain-care product; a body-care product, such as a hair care product (e.g. a shampoo, a leave-on or rinse-off hair conditioner, a coloring preparation or a hair spray, a color-care product, a hair shaping product, a dental care product), a disinfectant, an intimate care product; a cosmetic preparation (e.g. a skin cream or lotion, a vanishing cream or a deodorant or antiperspirant (e.g. a spray or roll on), a hair remover, a nail product, a skin cleansing, a makeup); or a skin-care product (e.g. a soap, a shower or bath mousse, oil or gel, or a hygiene product or a foot / hand care product); an air care product, such as an air freshener or a “ready to use” powdered air freshener which can be used in the home space (rooms, refrigerators, cupboards, shoes or car) and / or in a public space (halls, hotels, malls, etc..); or a home care product, such as a mold remover, a furniture care product, a wipe, a dish detergent or a hard-surface (e.g. a floor, bath, sanitary or a window-cleaning) detergent; a leather care product; a car care product, such as a car air-freshener, a polish, a wax or a plastic cleaner. Particularly, the perfumed consumer product may be a fabric care product, such as a liquid or solid detergent, a fabric softener, a liquid or solid scent booster, a dryer sheet, a fabric refresher, an ironing water, a hair care product (e.g. a shampoo, a leave-on or rinse-off hair conditioner), a disinfectant, an air care product, such as an air freshener, or a hard-surface detergent. More particularly, the perfumed consumer product may be a fabric care product, such as a liquid or solid detergent, a fabric softener, a liquid or solid scent booster, a dryer sheet, a fabric refresher, an ironing water, an air care product, such as an air freshener, or a hard-surface detergent.

[0165] According to a particular embodiment, the invention’s perfumed consumer product is in the form of a personal care, a home care or fabric care consumer product comprising ingredients that are common in personal, home or fabric care consumer products, in particular shower gels, shampoos, soaps, fabric detergents or softeners and all-purpose cleaners. The main functional constituents of perfumed consumer products are surfactants and / or softener components capable of cleaning and / or softening fabrics and / or textiles of varied nature, such as clothes, curtain fabrics, carpets and furniture fabrics, etc., or other home surfaces, skin or hair, and typically used in a large amount of water or water-based solvents. These are therefore formulations wherein the amount of water is typically comprised between 50 and 99% by weight of the perfumed consumer product with the exception of soaps or solid detergents, wherein the amount of water is at most 20%.

[0166] A more detailed description of such fabric cleaning and / or softening formulations is not warranted here, many descriptions of current liquid formulations can be found in the cleaner / fabric softener’s patent and other pertinent literature, such as for example the textbook of Louis Ho Tan Tai, “Detergents et Produits de Soins Corporels, Chapters 1 to 7 in particular, Dunod, Paris, 1999, or any other similar and / or more recent textbooks pertaining to the art of liquid softener and all-purpose cleaners formulations. A patent publication, WO 2010 / 105873, is also cited by way of example, in as much as it describes typical current ingredients, other than perfumes, of such liquid products, particularly on pages 9 to 21. Of course, many other examples of liquid cleaner and / or fabric softener formulations can be found in the literature. Any such liquid formulations, namely liquid fabric cleaners or conditioners and / or all-purpose cleaners, can be used in the here-described compositions. Other examples of fabric detergents or softener compositions into which the compounds of the invention can be incorporated are described in WO 97 / 34986 or in US patents 4,137,180 and 5,236,615 or EP 799 885. Other typical detergent and softening compositions which can be used are described in works such as Ullmann's Encyclopedia of Industrial Chemistry, Vol. 20, Wiley-VCH, Weinheim, pages 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.

[0167] According to a particular embodiment of the invention, the invention’s perfumed consumer product may be a liquid fabric softener comprising at least one compound of formula (I) and a fabric softener active base in amount comprised between 85 and 100% by weight, based on the total weight of the perfumed consumer product. The main constituent of the fabric softener active base is water or water-based solvents. The fabric softener active base may comprise dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts, Hamburg esterquat, triethanolamine quat, silicones and mixtures thereof. Optionally, component a) of the composition may further comprise a viscosity modifier in an amount comprised between 0.05 and 1% by weight, based on the total weight of the liquid base; preferably chosen from the group consisting of calcium chloride.

[0168] According to a particular embodiment of the invention, the invention’s consumer product is an all-purpose cleaner comprising at least one compound of formula (I) and an all- purpose cleaner active base in amount comprised between 85 and 100% by weight, based on the total weight of the consumer product. The main constituent of the all-purpose cleaner active base is water or water-based solvents. The all-purpose active base may comprise linear alkylbenzene sulfonates (LAS) in an amount comprised between 0 and 4%, preferably 1 and 2%, nonionic surfactant in an amount comprised between 0 and 8%, preferably 2 and 4% and acid such as citric acid in an amount comprised between 0.1 and 0.5%.

[0169] According to a particular embodiment of the invention, the invention’s consumer product is a liquid detergent comprising at least one compound of formula (I) and liquid detergent active base in amount comprised between 85 and 100% by weight, based on the total weight of the consumer product. The main constituent of the liquid detergent active base is water or water-based solvents. The liquid detergent active base may comprise anionic surfactants such as alkylbenzene sulfonates (ABS), linear alkylbenzene sulfonates (LAS), secondary alkyl sulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), sodium lauryl ether sulfates (SLES), methyl ester sulfonates (MES); nonionic surfactants such as alkyl amines, alkanolamides, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, alkyl polyglucosamides; or mixtures thereof.

[0170] According to a particular embodiment of the invention, the invention’s consumer product is a solid detergent comprising at least one compound of formula (I) and a solid detergent active base in amount comprised between 85 and 100% by weight, based on the total weight of the consumer product. The solid detergent active base may comprise at least one surfactant chosen from the group consisting of anionic, nonionic, cationic, zwiterionic surfactant and mixtures thereof. The surfactant in the solid detergent active base is preferably chosen from the group consisting of linear alkene benzene sulfonates (LABS), sodium laureth sulfate, sodium lauryl ether sulfates (SLES), sodium lauryl sulfate (SLS), alpha olefin sulfonates (AOS), methyl ester sulfonates (MES), alkyl polyglycosides (APG), primary alcohol ethoxylates and in particular lauryl alcohol ethoxylates (LAE), primary alcohol sulfonates (PAS), soap and mixtures thereof. The soild detergent active base may comprise a further component, commonly used in powder detergent consumer product, selected from the group consisting of bleaching agents such as EDTA (tetraacetylethylenediamine); buffering agent; builders such as zeolites, sodium carbonate or mixture thereof; soil release or soil suspension polymers; granulated enzyme particles such as cellulase, lipase, protease, mannanase, pectinase or mixtures thereof; corrosion inhibitor; antifoaming; sud suppressing agents; dyes; fillers such as sodium silicate, sodium sulfate or mixture thereof; source of hydrogen peroxide such as sodium percarbonate or sodium perborate; and mixtures thereof.

[0171] The proportions in which the perfuming composition according to the invention can be incorporated into the various aforementioned articles or compositions vary within a wide range of values. These values are dependent upon the nature of the article or product to be perfumed and on the desired olfactory effect as well as the nature of the co-ingredients in a given composition when the compounds according to the invention are mixed with perfuming co-ingredients, solvents or additives commonly used in the art.

[0172] For example, in the case of perfuming compositions, typical concentrations are in the order of 0.001 % to 10 % by weight, or even more, of the compounds of the invention based on the weight of the composition into which they are incorporated. In the case of perfumed consumer products, typical concentrations are in the order of 0.0001 % to 1 % by weight, or even more, preferably between 0.05 % to 0.8 %, even more preferably between 0.1 % and 0.5 % of the compounds of the invention based on the weight of the consumer product into which they are incorporated.

[0173] Another aspect of the invention concerns the use of a perfuming composition according to the invention for improving, enhancing, conferring and / or modifying the fragrance impression and / or fragrance intensity of a consumer product.

[0174] Another aspect of the invention concerns a method for improving, enhancing, conferring and / or modifying the fragrance impression and / or fragrance intensity of a consumer product, comprising the step of adding the perfuming composition according to the invention to a consumer product.

[0175] Moreover, the present invention relates to a compound of formula (I). An object of the invention is a compound of formula (I"') as defined herein. In an embodiment of the compound of formula (I'"), methyl 2-(8-methoxy-8-oxooctyl)thiazolidine-4-carboxylate, 2- (2,4,4-trimethylpentyl)thiazolidine-4-carboxylic acid, ethyl 2-(2,4,4- trimethylpentyl)thiazolidine-4-carboxylate, 2-(l-(4-isopropylphenyl)propan-2-yl)thiazolidine-

[0176] 4-carboxylic acid, 2-(2-phenylpropyl)thiazolidine-4-carboxylic acid and 2-(2,6-dimethylhept-

[0177] 5-en-l-yl)thiazolidine-4-carboxylic acid are excluded.

[0178] So, another object of the invention is a compound of formula in the form of any one of its stereoisomers or a mixture thereof, and wherein

[0179] R1comprises between 8 and 18 carbon atoms and is a group of formula wherein the dashed line represents a single or a double bond; R3is a C4-12 hydrocarbon group optionally comprising one or two oxygen atoms; R4and R5, independently from each other; are a hydrogen atom or a C1-6 alkyl group; or R3and R4or R3and R5, when taken together, form a C5-15 cycloalkyl, C5-15 cycloalkenyl, C4-14 heterocycloalkyl or C4-14 heterocycloalkenyl group, each optionally substituted with one or more of a C1-15 alkyl, Ci-s alkenyl C1-15 alkoxy, C3-15 cycloalkyl and / or C5-15 cycloalkenyl, each optionally substituted with one or more of a C1-8 alkyl, C1-8 alkoxy, carboxylic acid and / or C1-4 carboxylic ester group; wherein the heteroatom represents one or two oxygen atoms;

[0180] R2represents a hydrogen atom; n is 1, 2, 3 or 4;

[0181] X is an oxygen atom or a NR7group wherein R7is a hydrogen atom or a C1-6 alkyl group;

[0182] R6is a hydrogen atom, a sodium, potassium or ammonium cation or a C1-16 hydrocarbon group, optionally containing one to nine oxygen atoms; provided that methyl 2-(8-methoxy-8-oxooctyl)thiazolidine-4-carboxylate, 2-(2,4,4- trimethylpentyl)thiazolidine-4-carboxylic acid, ethyl 2-(2,4,4-trimethylpentyl)thiazolidine-4- carboxylate, 2-(l-(4-isopropylphenyl)propan-2-yl)thiazolidine-4-carboxylic acid, 2-(2- phenylpropyl)thiazolidine-4-carboxylic acid and 2-(2,6-dimethylhept-5-en-l-yl)thiazolidine- 4-carboxylic acid are excluded.

[0183] According to any one of the above embodiments of the invention, when R6is a hydrogen atom, then at least one group among R4and R5is a C1-6 alkyl group. Particularly, when R6is a hydrogen atom, then at least one group among R4and R5is a C1-4 alkyl group. Particularly, when R6is a hydrogen atom, then at least one group among R4and R5is a C1-3 alkyl group. Particularly, when R6is a hydrogen atom, then at least one group among R4and R5is a methyl or ethyl group. Even more particularly, when R6is a hydrogen atom, then at least one group among R4and R5is a methyl group.

[0184] According to any one of the above embodiments of the invention, at least one group among R4and R5is a C1-6 alkyl group. Particularly, at least one group among R4and R5is a C1-4 alkyl group. Particularly, at least one group among R4and R5is a C1-3 alkyl group. Particularly, at least one group among R4and R5is a methyl or ethyl group. Even more particularly, at least one group among R4and R5is a methyl group.

[0185] Another particular object of the invention is a compound of formula in the form of any one of its stereoisomers or a mixture thereof, and wherein n is 1, 2, 3 or 4;

[0186] X is an oxygen atom or a NR7group wherein R7is a hydrogen atom or a Ci-6 alkyl group;

[0187] R6is a hydrogen atom, a sodium, potassium or ammonium cation or a Ci-i6 hydrocarbon group, optionally containing one to nine oxygen atoms;

[0188] R8is a C3-9 hydrocarbon group optionally comprising one oxygen atom; R9and R10, independently from each other, are a hydrogen atom or a methyl group; or R8and R10, when taken together, form a C5-8 cycloalkenyl group optionally substituted with one or more of a C1-6 alkyl or C2-6 alkenyl group.

[0189] For the sake of clarity, by the wavy bond in compound of formula (la), or the similar, it is meant the normal meaning understood by a person skilled in the art, i.e. that the double bond may have a cis configuration corresponding to the Z isomer, a trans configuration corresponding to the E isomer or a mixture thereof. In other words, the compound of, compound of formula (la) can be in the form of its E or Z isomer or of a mixture thereof, e.g. the invention comprises compositions of matter consisting of one or more compounds of formula (la), having the same chemical structure but differing by the configuration of the double bond. In particular, compound (la) can be in the form of a mixture consisting of isomers E and Z and wherein said isomers Z represent at least 50 % of the total mixture, or even at least 75% (i.e a mixture Z / E comprised between 75 / 25 and 100 / 0).

[0190] According to any embodiment of the invention, R8is a C3-9 alkyl group or a C3-9 alkenyl group; each optionally substituted by a hydroxy group. Particularly, R8is a C5-9 alkyl group optionally substituted by a hydroxy group or a C5-8 linear alkenyl group. Even more particularly, R8is a C5-7 alkyl group optionally substituted by a hydroxy group.

[0191] According to any embodiment of the invention, R10is a hydrogen atom.

[0192] According to any embodiment of the invention, R8and R10, when taken together, form a C5-7 cycloalkenyl group optionally substituted with one or more of a C1-6 alkyl or C2-6 alkenyl group. Particularly, R8and R10, when taken together, form a C5-7 cycloalkenyl group optionally substituted with one or more of a C1-4 alkyl or C2-4 alkenyl group. Particularly, R8and R10, when taken together, form a C5-7 cycloalkenyl group optionally substituted with one or two or three of a C1-4 alkyl or C2-4 alkenyl group. Particularly, R8and R10, when taken together, form a C5-6 cycloalkenyl group optionally substituted with one or two or three of a C1-4 alkyl or C2-4 alkenyl group. Particularly, R8and R10, when taken together, form a C5-6 cycloalkenyl group optionally substituted with one or two of a C1-3 alkyl group. Even more particularly, R8and R10, when taken together, form a C5-6 cycloalkenyl group optionally substituted with one or two methyl groups.

[0193] Another particular object of the invention is a compound of formula (III) as defined above.

[0194] Another particular object of the invention is a compound of formula (IV) as defined above.

[0195] According to any embodiment of the invention, the compounds of formula (I), (la), (III) or (IV) are selected from the group consisting of 2-(undecan-2-yl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(undecan-2-yl)thiazolidine-4-carboxylate, sodium 2-(undecan-2- yl)thiazolidine-4-carboxylate, 2-(6-methyl-5-hepten-2-yl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(6-methyl-5-hepten-2-yl)thiazolidine-4-carboxylate, 2-(3- and 4-(4-methyl- 3-pentenyl)-3-cyclohexenyl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(3- and 4-(4- methyl-3-pentenyl)-3-cyclohexenyl)thiazolidine-4-carboxylate, 2-(2-(4-methyl-3- cyclohexenyl)propyl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(2-(4-methyl-3- cyclohexenyl)propyl)thiazolidine-4-carboxylate, 2-(non-3 -en- 1 -yl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(non-3-en-l-yl)thiazolidine-4-carboxylate, 2-(undec-3-en-l- yl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(undec-3-en-l-yl)thiazolidine-4- carboxylate, 2-(2-(4,4-dimethyl-l-cyclohexenyl)ethyl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(2-(4,4-dimethyl-l-cyclohexenyl)ethyl)thiazolidine-4-carboxylate, methyl or ethyl 2-(l-(4-isopropylphenyl)propan-2-yl)thiazolidine-4-carboxylate, methyl or ethyl 2-(2- phenylpropyl)thiazolidine-4-carboxylate, 2-(2,4-dimethylcyclohex-3-en-l-yl)thiazolidine-4- carboxylic acid, methyl or ethyl 2-(2,4-dimethylcyclohex-3-en-l-yl)thiazolidine-4- carboxylate, methyl or ethyl 2-nonylthiazolidine-4-carboxylate, 2-(4,8-dimethylnon-3-en-l- yl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(4,8-dimethylnon-3-en-l-yl)thiazolidine- 4-carboxylate, 2-(6-hydroxy-2,6-dimethylheptyl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(6-hydroxy-2,6-dimethylheptyl)thiazolidine-4-carboxylate, 2-(3-methyl-4-(4- methylphenyl)but-3-en-l-yl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(3-methyl-4-(4- methylphenyl)but-3-en-l-yl)thiazolidine-4-carboxylate, 2-(2-(l,l- or 3,3-dimethyl-2,3- dihydro-lH-inden-5- or 4-yl)ethyl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(2-(l,l- or 3,3-dimethyl-2,3-dihydro-lH-inden-5- or 4-yl)ethyl)thiazolidine-4-carboxylate, 2-methyl- 2-(2-(2,6,6-trimethylcyclohex-l-en-l-yl)ethyl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-methyl-2-(2-(2, 6, 6-trimethyl cyclohex- 1 -en- 1 -yl)ethyl)thiazolidine-4-carboxylate, 2-(4- hydroxyphenethyl)-2-methylthiazolidine-4-carboxylic acid, methyl or ethyl 2-(4- hydroxyphenethyl)-2-methylthiazolidine-4-carboxylate, 6-pentyl-l-thia-4- azaspiro[4.4]nonane-3-carboxylic acid, methyl or ethyl 6-pentyl-l-thia-4- azaspiro[4.4]nonane-3-carboxylate, 7-methyl-2H,4H-spiro[benzo[b][l,4]dioxepine-3,2'- thiazolidine]-4'-carboxylic acid, methyl or ethyl 7-methyl-2H,4H- spiro[benzo[b][l,4]dioxepine-3,2'-thiazolidine]-4'-carboxylate or oxybis(ethane-2,l-diyl) bis(2-(non-3-en-l-yl)thiazolidine-4-carboxylate) in the form of either one of its stereoisomers and / or a mixture thereof.

[0196] In a further aspect, the present invention also relates to the use of precursor compounds of formula (I) for releasing an aldehyde or a ketone of formula wherein the compound of formula (II) comprises at least 8 carbon atoms;

[0197] R1is a phenyl, a benzyl, a benzo[d][l,3]dioxole or a naphthyl group; with the phenyl and benzyl group being optionally substituted with one or more of a Ci-s alkyl, Ci-s alkoxy, hydroxy and / or Ci-4 carboxylic ester group, or R1is a group of formula wherein the dashed line represents a single or a double bond; R3is a C2-12 hydrocarbon group optionally comprising one or two oxygen atoms; R4and R5, independently from each other, are a hydrogen atom or a C1-6 alkyl group; or R3and R5or R3and R4, when taken together, form a C5-15 cycloalkyl, C5-15 cycloalkenyl, C4-14 heterocycloalkyl or C4-14 heterocycloalkenyl group, each optionally substituted with one or more of a C1-15 hydrocarbon, optionally comprising one or more oxygen atoms, wherein the heteroatom represents one or more oxygen atoms;

[0198] R2represents a hydrogen atom or a C1-15 hydrocarbon group;

[0199] R1and R2, when taken together, form a C5-15 cycloalkyl, C5-15 cycloalkenyl group wherein the double bond is not conjugated with the ketone functional group, C4-14 heterocycloalkyl or C4-14 heterocycloalkenyl group wherein the double bond is not conjugated with the ketone functional group, each optionally substituted with one or more of a C1-15 alkyl, C1-15 alkoxy, C3-15 cycloalkyl, C5-15 cycloalkenyl, Ce-io aryl and / or Ce-io aryloxy group, each optionally substituted with one or more of a Ci-s alkyl, C1-8 alkoxy and / or C1-4 carboxylic ester group, wherein the heteroatom represents one or more oxygen atoms; wherein the precursor compound comprises a compound of formula in the form of any one of its stereoisomers or a mixture thereof, and wherein R1and R2have the same meaning as defined above; n is 1, 2, 3 or 4; X is an oxygen atom or a NR7group wherein R7is a hydrogen atom or a Ci-6 alkyl group; R6is a hydrogen atom, a sodium, potassium or ammonium cation or a Ci-i6 hydrocarbon group optionally containing one to nine oxygen atoms; by exposing the precursor compound of formula (I) to trace of water.

[0200] In a further aspect, the present invention relates to the use of at least one compound of formula (I) as defined above to confer, enhance, improve or modify the odor properties of a perfuming composition, the air surrounding the perfuming composition, a surface, or of a perfumed article, comprising adding to the composition or article or contacting or treating the surface with an effective amount of at least one compound of formula (I) as defined above. The term “surface”, as used herein may refer to a user’s skin, hair, a textile, or hard surface, on to which, a perfume composition comprising or containing the at least one compound of formula (I) is applied. In a further aspect, the present invention relates to the use of at least one compound of formula (I) as defined above for intensifying or prolonging the diffusion effect, and / or perception of the characteristic fragrance of an aldehyde or a ketone of formula (II) as defined above, on a surface, wherein the surface is treated with at least one compound of formula (I) as defined above, or with a composition or article containing the at least one compound of formula (I), under conditions susceptible of allowing the release of the aldehyde or a ketone of formula (II) over time.

[0201] The compounds of formula (I) can be prepared according to standard methods known in the art as described herein-below.

[0202] Examples

[0203] The invention will now be described in further detail by way of the following examples, wherein the abbreviations have the usual meaning in the art, the temperatures are indicated in degrees centigrade (°C). Reactions were carried out in standard glassware under N2. Commercially available reagents and solvents were used without further purification. If not specified otherwise, NMR spectra were acquired in CDCh at room temperature using either a Bruker Avance III 500 spectrometer operating at 500 MHz (1H) and 125.8 MHz (13C) or a Bruker Avance III 600 spectrometer operating at 600 MHz (' H) and 150.9 MHz (13C). Spectra were internally referenced relative to tetramethyl silane (0.0 ppm). 'H-NMR chemical shifts ( <5) are expressed in ppm, coupling constants (J) are indicated in Hz with the following multiplicities: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; br., broad signal (indicating unresolved couplings).13C-NMR chemical shifts ( <5) are expressed in ppm, signals marked with an asterisk (*) have been tentatively assigned.

[0204] Although specific conformations or configurations are indicated for some of the compounds, this is not meant to limit the use of these compounds to the isomers described.

[0205] Cysteine naturally occurs as L-(A’)-cysteine. However, its non-natural enantiomer D- GV)-cysteine and the racemic mixture are also readily available. Both L- and D-cysteine, as well as mixtures thereof, are expected to provide a comparable performance in the context of the present invention.

[0206] Preparation of comparative compounds Synthesis of ethyl (^)-(4S)-2-(6-methyl-5-hepten-2-yl)oxazolidine-4-carboxylate (Compound A)

[0207] 2,6-Dimethyl-5-heptenal (Melonal, 1.59 g, 10.0 mmol) was added to a solution of ethyl L- serinate hydrochloride (3.39 g, 20.0 mmol) and triethylamine (TEA, 3.0 mL, 22.0 mmol) in ethanol (50 mL). Then anhydrous MgSCL (2.00 g) was added and the mixture heated to reflux (80°C) for 17 h. After cooling to room temperature, the solvent was removed under reduced pressure. Then ethyl acetate (100 mL) was added, and the solution washed with a saturated aqueous solution of NaHCCL (50 mL). The aqueous phase was re-extracted with ethyl acetate (100 mL) and the combined organic phases washed with a saturated aqueous solution of NaCl (50 mL), dried (Na2SO4), filtered and concentrated. Bulb-to-bulb distillation (110°C, 0.66 mbar) to remove remaining volatiles afforded 2.60 g (quant.) of the target compound as a mixture of four diastereoisomers (ca. 35:33:17:15).

[0208] 'H-NMR (500 MHz, major isomers): 5.13-5.06 (m, 1 H), 4.29-4.15 (m, 3 H), 3.95-3.85 (m, 2 H), 3.79-3.72 (m, 1 H), 2.15-1.90 (m, 2 H), 1.85-1.71 (m, 1 H), 1.71-1.53 (m, 1 H), 1.68 (5, 3 H), 1.61 (5, 3 H), 1.34-1.12 (m, 1 H), 1.29 (t, J= 7.2, 3 H), 1.02 (d, J= 6.7, 3 H), NH not assigned.

[0209] 'H-NMR (500 MHz, minor isomers): 5.13-5.06 (m, 1 H), 4.42 (2 d, J = 5.7 and 5.4, 1 H), 4.29-4.15 (m, 2 H), 4.12 (2 t, J= 7.9 and 8.0, 1 H), 4.00-3.94 (m, 1 H), 3.74-3.65 (m, 1 H), 2.15-1.90 (m, 2 H), 1.71-1.53 (m, 2 H), 1.68 (5, 3 H), 1.61 (5, 3 H), 1.34-1.12 (m, 1 H), 1.29 t, J= 7.2, 3 H), 0.96 (d, J= 6.7, 3 H), NH not assigned.

[0210] 13C-NMR (125.8 MHz, major isomers): 172.52, 131.74 and 131.66, 124.26 and 124.22, 96.99 and 96.91, 68.18 and 68.15, 61.63, 59.69 and 59.63, 35.89 and 35.72, 32.74 and 32.60, 25.71, 25.39 and 25.30, 17.69 and 17.68, 14.63 and 14.57, 14.17.

[0211] 13C-NMR (125.8 MHz, minor isomers): 172.69 and 172.68, 131.59 and 131.55, 124.42 and 124.39, 96.42 and 96.29, 68.26 and 68.22, 61.35, 59.21 and 59.19, 36.70 and 36.61, 32.58 and 32.38, 25.71, 25.39 and 25.34, 17.71, 14.68 and 14.33, 14.19.

[0212] Synthesis of ethyl (±)-(4S)-2-(undecan-2-yl)oxazolidine-4-carboxylate (Compound B)

[0213] (±)-2 -Methylundecanal (1.84 g, 10.0 mmol) was added to a solution of ethyl L-serinate hydrochloride (3.39 g, 20.0 mmol) and TEA (3.0 mL, 22.0 mmol) in ethanol (50 mL). Then MgSCL (2.00 g) was added and the mixture heated to reflux (80°C) for 17 h. After cooling to room temperature, the solvent was removed under reduced pressure. Then demineralized water (50 mL) was added to the residue, and the mixture extracted with ethyl aetate (2x 100 mL). The combined organic phases were washed with a saturated aqueous solution of NaCl (2x 50 mL), dried (Na2SC>4), filtered and concentrated. Bulb-to-bulb distillation (120°C, 0.68 mbar) gave 2.68 g (89%) of the target compound as a mixture of four diastereoisomers (ca. 34:33:17:16).

[0214] 'H-NMR (500 MHz, major isomers): 4.29-4.18 (m, 2 H), 4.18 (d, J = 5.8, 1 H), 3.95-3.86 (m, 2 H), 3.80-3.72 (m, 1 H), 2.63 (br. s, 1 H), 1.82-1.69 (m, 1 H), 1.69-1.47 (m, 1 H), 1.46- 1.17 (m, 18 H), 1.00 (dd, J= 6.7, 1.3, 3 H), 0.88 (t, J= 6.9, 3 H).

[0215] 'H-NMR (500 MHz, minor isomers): 4.43-4.39 (m, 1 H), 4.29-4.18 (m, 2 H), 4.11 (dt, J = 8.0, 4.5, 1 H), 4.01-3.94 (m, 1 H), 3.73-3.67 (m, 1 H), 2.63 (br. s, 1 H), 1.69-1.47 (m, 2 H), 1.46-1.17 (m, 18 H), 0.94 (dd, J= 6.7, 1.3, 3 H), 0.88 (t, J= 6.9, 3 H).

[0216] 13C-NMR (125.8 MHz, major isomers): 172.54 and 172.52, 97.01 and 96.99, 68.19 and 68.16, 61.63, 59.69 and 59.64, 36.48 and 36.39, 32.78 and 32.65, 31.91, 29.86 and 29.85, 29.62, 29.34, 27.03 and 26.95, 22.69, 14.74 and 14.60, 14.17, 14.12.

[0217] 13C-NMR (125.8 MHz, minor isomers): 172.70, 96.48 and 96.36, 68.26 and 68.22, 61.35, 59.23 and 59.21, 37.26 and 37.18, 32.58 and 32.39, 31.91, 29.90, 29.62, 29.34, 27.05 and 26.97, 22.69, 14.73 and 14.42, 14.20, 14.12.

[0218] Synthesis of ethyl (±)-(4R)-3-acetyl-2-(undecan-2-yl)thiazolidine-4-carboxylate (Compound Q

[0219] Iodine (0.05 g, 0.2 mmol) was added to ethyl (±)-(4 / ?)-2-(undecan-2-yl)thiazolidine-4- carboxylate (Compound 4, prepared as described in Example 1 below, 0.63 g, 2.0 mmol) in acetic anhydride (1.9 mL, 20.0 mmol). The mixture was stirred at room temperature for 2 h before w-pentane (50 mL) and a saturated aqueous solution of NaHCCL (25 mL) were added. The phases were separated and the aqueous phase extracted with w-pentane (50 mL). The combined organic phases were washed with saturated aqueous solutions of NaHCCL (2x 25 mL) and NaCl (25 mL), dried (Na2SO4), filtered and concentrated. Column chromatography (SiCh. « -heptane / ethyl acetate 7:3) afforded 0.06 g (8%) of the target compound as a mixture of two diastereoisomers (ca. 63:37) and 0.53 g (74%) of the target compound as a mixture of four diastereoisomers (ca. 33:27:21 :19).

[0220] 'H-NMR (500 MHz, major isomers): 5.05 and 4.94 (t, J= 8.5, 8.6, 1 H), 4.80 and 4.69 (d, J = 7.4, 9.6, 1 H), 4.32-4.14 (m, 2 H), 3.34-3.14 (m, 2 H), 2.20 and 2.19 (5, 3 H), 1.95-1.84 (m, 0.5 H), 1.84-1.68 (m, 1 H), 1.65-1.52 (m, 0.5 H), 1.51-1.18 (m, 17 H), 1.18-1.08 (m, 1 H), 1.10 and 1.06 (d, J= 6.7, 6.6, 3 H), 0.88 (t, J= 6.7, 3 H). 'H-NMR (500 MHz, minor isomers): 5.41-5.35 (m, 1 H), 4.74-4.67 (m, 1 H), 4.32-4.14 (m, 2 H), 3.45-3.25 (m, 2 H), 2.11 and 2.10 (5, 3 H), 2.08-1.99 (m, 0.5 H), 1.84-1.68 (m, 0.5 H), 1.65-1.52 (m, 0.5 H), 1.51-1.18 (m, 17.5 H), 1.18-1.08 (m, 1 H), 1.00 and 0.93 (d, J = 6.7, 6.6, 3 H), 0.88 (t, J= 6.7, 3 H).

[0221] 13C-NMR (125.8 MHz, major isomers): 170.73 and 170.43, 169.51 and 169.37, 71.63 and 71.31, 63.08 and 62.27, 61.55 and 61.49, 40.28 and 40.12, 34.43 and 33.57, 32.10 and 31.85, 31.90, 29.91, 29.80 and 29.64, 29.59, 29.33 and 29.31, 27.57 and 26.80, 22.69, 22.63 and 22.55, 17.04 and 15.60, 14.12.

[0222] 13C-NMR (125.8 MHz, minor isomers): 170.66 and 170.38, 169.90 and 169.67, 70.46 and 69.81, 63.89 and 63.58, 62.13 and 62.10, 39.46 and 38.00, 34.03 and 33.50, 33.50 and 33.26, 31.90, 29.91 and 29.80, 29.72, 29.59, 29.33, 27.49 and 26.85, 23.09 and 22.77, 22.69, 16.54 and 15.41, 14.12.

[0223] Synthesis of ethyl (±)-(4S)-5,5-dimethyl-2-(undecan-2-yl)thiazolidine-4-carboxylate (Compound D)

[0224] First step. Following a literature procedure for the preparation of a similar compound (see: M. Chvapil et al. Connective Tissue Research, 2005, Vol. 46, pages 242-250), a suspension of (<S)-2-amino-3-mercapto-3-methylbutanoic acid (D-penicillamine, 2.50 g, 16.4 mmol) in ethanol (50 mL) was cooled on an ice bath to 0°C before thionyl chloride (12.5 mL, 172.3 mmol) was added dropwise under a flow of nitrogen during 45 min. The reaction temperature was kept at 3-4°C during the introduction. After stirring at room temperature for 2 d, the solution was cooled to 0°C with an ice bath and more thionyl chloride (2.5 mL) was added dropwise. After warming to room temperature, the reaction mixture was left stirring for 1 d, then heated to reflux (80°C) for 3 h, while washing the nitrogen flow through an aqueous solution of NaOH (5%). Then the ethanol / thionyl chloride mixture was distilled off (77°C), and the reaction mixture concentrated to ca. 20 mL. After cooling to room temperature, diethyl ether (50 mL) was added in two portions. Then w-pentane (50 mL) was added and a precipitate was formed. The w-pentane was decanted, the solid washed with w-pentane. A mixture of methanol / diethyl ether (10 mL) was added and the product stored in the freezer. The solvent was removed and the solid dried under vacuum (0.7 mbar) to yield 3.57 g of ethyl (S)-2-amino-3-mercapto-3-methylbutanoate hydrochloride as a crude product, which was used without further purification for the next reaction step. Second step. (±)-2 -Methylundecanal (1.38 g, 7.5 mmol) was added to a solution of crude ethyl (<S)-2-amino-3-mercapto-3-methylbutanoate hydrochloride (1.76 g, 8.3 mmol) and TEA (1.3 mL, 9.0 mmol) in ethanol (50 mL). The mixture was heated under reflux (80°C) for 2 h. After cooling to room temperature, the solvent was removed under reduced pressure. Then ethyl acetate (100 mL) was added, and the organic layer washed with a saturated aqueous solution of NaHCCL (50 mL). The aqueous phase was re-extracted with ethyl acetate (100 mL) and the combined organic phases washed with a saturated aqueous solution of NaCl (50 mL). After separating the phases by centrifugation of small portions, the organic phase was dried (ISfeSCL), filtered and concentrated. Column chromatography (1.53 g, SiCh. « -heptane / ethyl acetate 95:5) and combining the product fractions gave 0.70 g (72%) of the target compound as a mixture of four diastereoisomers (ca. 39:34:14:13).

[0225] 'H-NMR (500 MHz, major isomers): 4.64-4.56 and 4.56-4.49 (m, 1 H), 4.30-4.17 (m, 2 H), 3.63-3.56 (m, 1 H), 1.90-1.80 and 1.80-1.70 (m, 1 H), 1.69-1.50 and 1.48-1.14 (m, 23 H), 1.30 (t, J= 7.2, 3 H), 1.08 and 1.00 (d, J= 6.7, 3 H), 0.88 (t, J= 6.9, 3 H).

[0226] 'H-NMR (500 MHz, minor isomers): 4.50 and 4.44 (d, J = 8.0, 1 H), 4.30-4.17 (m, 2 H), 3.67-3.64 (m, 1 H), 1.69-1.50 and 1.48-1.14 (m, 24 H), 1.30 (t, J = 7.2, 3 H), 0.99 and 0.90 (d, J= 6.7, 3 H), 0.88 (t, J= 6.9, 3 H).

[0227] 13C-NMR (125.8 MHz, major isomers): 169.61 and 169.59, 74.33 and 74.27, 74.14 and 74.13, 61.15, 57.58 and 57.32, 38.73 and 37.96, 34.96 and 34.70, 31.90, 29.79, 29.61 and 29.60 (2 C), 29.40 and 29.35, 29.33, 28.44 and 28.37, 27.03 and 26.88, 22.69, 16.59 and 16.35, 14.31, 14.12.

[0228] 13C-NMR (125.8 MHz, minor isomers): 169.98 and 169.97, 73.24 and 73.06, 72.80 and 72.76, 61.13, 58.30 and 58.18, 41.35 and 41.30, 34.15 and 33.77, 31.90, 29.94 and 29.90, 29.68 and 29.65, 29.63 and 29.61, 29.34, 27.75 and 27.73, 27.05, 27.07 and 26.96, 22.69, 16.70 and 16.08, 14.30, 14.12.

[0229] Example 1

[0230] Preparation of compounds according to formula (I)

[0231] General method

[0232] The compound of formula (II) to be released (15.0 mmol) was added to a solution of ethyl L- cysteinate hydrochloride (3.13 g, 16.5 mmol) and triethylamine (TEA, 2.5 mL, 18.0 mmol) in ethanol (50 mL). The mixture was heated under reflux (80°C) for 2 h. After cooling to room temperature, the solvent was removed under reduced pressure. Then ethyl acetate (100 mL) was added, and the organic layer washed with a saturated aqueous solution of NaHCCL (50 mL). The aqueous phase was re-extracted with ethyl acetate (100 mL) and the combined organic phases washed with a saturated aqueous solution of NaCl (50 mL), dried (N zSCL), filtered and concentrated to give the crude target compound.

[0233] Synthesis of ethyl (±)-(4R)-2-(l-(4-isopropylphenyl)propan-2-yl)thiazolidine-4-carboxylate (Compound 1)

[0234] The compound was prepared as described in the general method using (±)-3-(4- isopropylphenyl)-2-methylpropanal (Cyclamen aldehyde, 2.85 g) as the compound of formula (II). Column chromatography (SiCh. n-heptane / ethyl acetate 9:1, then 8:2) gave 4.29 g (87%) of the target compound as a mixture of four diastereoisomers (ca. 37:33: 17: 13).

[0235] 'H-NMR (500 MHz, major isomers): 7.17-7.06 (m, 4 H), 4.47 (d, J= 6.4, 1 H), 4.31-4.17 (m, 2 H), 3.80 and 3.79 (d, J= 7.1, 1 H), 3.30 and 3.29 (t, J= 10.3 and 10.1, 1 H), 2.93-2.83 (m, 2 H), 2.79 and 2.77 (t, J = 9.9, 1 H), 2.56-2.46 (m, 1 H), 2.29-2.11 (m, 1 H), 1.34- 1.26 (m, 3 H), 1.24 (d, J= 7.1, 6 H), 1.05 and 1.01 (d, J = 6.7, 3 H), NH not assigned.

[0236] 'H-NMR (500 MHz, minor isomers): 7.17-7.06 (m, 4 H), 4.59 and 4.58 (d, J = 7.1, 1 H), 4.31-4.17 (m, 2 H), 4.11 and 4.07 (t, J = 6.6, 1 H), 3.26-3.18 (m, 1 H), 3.05-2.82 (m, 3 H), 2.44-2.35 (m, 1 H), 2.06-1.90 (m, 1 H), 1.34-1.26 (m, 3 H), 1.23 (d, J = 7.1, 6 H), 0.97 and 0.92 (d, J=-f 3 H), NH not assigned.

[0237] 13C-NMR (125.8 MHz, major isomers): 171.40 and 171.35, 146.67 and 146.62, 137.00 and 136.98, 129.17 and 129.10, 126.32, 76.27 and 76.19, 65.49 and 65.39, 61.56 and 61.55, 41.02 and 41.01, 40.04 and 39.43, 37.74 and 37.50, 33.69, 24.05, 16.76 and 16.13, 14.16.

[0238] 13C-NMR (125.8 MHz, minor isomers): 171.74, 146.47 and 146.39, 137.50 and 137.46, 129.20, 126.27 and 126.24, 75.11 and 74.84, 64.61 and 64.55, 61.51 and 61.50, 42.07 and 41.78, 40.52 and 40.15, 37.50 and 37.45, 33.68, 24.05, 16.73 and 16.00, 14.16.

[0239] Synthesis of ethyl (^)-(4R)-2-(6-methyl-5-hepten-2-yl)thiazolidine-4-carboxylate (Compound

[0240] 2) The compound was prepared as described in the general method using Melonal (2.40 g) as the compound of formula (II). Column chromatography (SiCh. w-heptane / ethyl acetate 9:1, then 8:2) gave a total of 3.38 g (83%) of the target compound as a mixture of four diastereoisomers (ca. 41:31:18:10).

[0241] 'H-NMR (600 MHz, major isomers): 5.14-5.05 (m, 1 H), 4.49 and 4.43 (d, J= 6.6, 6.9, 1 H), 4.30-4.17 (m, 2 H), 3.84-3.75 (m, 1 H), 3.28 and 3.27 (dd, J= 10.4, 6.9, 1 H), 2.76 and 2.74 (t, J = 9.8, 1 H), 2.23 (br. s, 1 H), 2.13-2.04 (m, 1 H), 2.04-1.90 (m, 1.5 H), 1.90- 1.82 (m, 0.5 H), 1.80-1.59 (m, 0.5 H), 1.69 and 1.68 (5, 3 H), 1.61 and 1.60 (5, 3 H), 1.58-1.50 (m, 0.5 H), 1.42-1.24 (m, 1 H), 1.30 (t, J= 7.1, 3 H), 1.12 and 1.06 (d, J= 6.9 and 6.5, 3 H).

[0242] 'H-NMR (600 MHz, minor isomers): 5.14-5.05 (m, 1 H), 4.56 and 4.52 (d, J= 7.3, 7.7, 1 H), 4.30-4.17 (m, 2 H), 4.12-4.04 (m, 1 H), 3.19 and 3.18 (t, J = 10.2, 1 H), 3.02 and 3.01 (dd, J= 10.4, 6.2, 1 H), 2.23 (br. s, 1 H), 2.13-2.04 (m, 1 H), 2.04-1.90 (m, 1 H), 1.80- 1.59 (m, 1.5 H), 1.69 and 1.68 (5, 3 H), 1.61 and 1.60 (5, 3 H), 1.58-1.50 (m, 0.5 H), 1.30 (f, J= 7.1, 3 H), 1.25-1.17 (m, 1 H), 1.04 and 0.97 (d, J= 6.9 and 6.5, 3 H).

[0243] 13C-NMR (150.9 MHz, major isomers): 171.43 and 171.41, 131.87 and 131.85, 124.04 and 124.02, 77.08 and 77.03, 65.45, 61.54, 37.80 and 37.11, 37.57 and 37.39, 35.12 and 35.00, 25.72, 25.42 and 25.28, 17.72 and 17.71, 16.91 and 16.52, 14.17.

[0244] 13C-NMR (150.9 MHz, minor isomers): 171.82 and 171.80, 131.62 and 131.58, 124.37 and 124.30, 75.91 and 75.71, 64.46 and 64.43, 61.46, 39.47 and 39.01, 37.32 and 37.20, 34.71 and 34.27, 25.72, 25.41 and 25.38, 17.10, 16.86 and 16.20, 14.17.

[0245] Synthesis of (±)-(4R)-2-(6-methyl-5-hepten-2-yl)thiazolidine-4-carboxylic acid (Compound 3)

[0246] Melonal (3.19 g, 20.0 mmol) was added to a suspension of L-cysteine (2.44 g, 20.0 mmol) in ethanol (50 mL). The reaction mixture was heated under reflux for 24 h. After filtering at elevated temperature and cooling to room temperature, the product crystallized. The mixture was cooled on an ice bath, filtered and washed with a minimum of ice-cold ethanol. Recrystallization of the filtrate in ethanol and drying in a desiccator (0.8 mbar) afforded a total of 2.15 g (44%) of the target compound as a mixture of four diastereoisomers (ca. 38:31:16:15).

[0247] 'H-NMR (600 MHz, DMSO-d6, major isomers): 5.14-5.04 (m, 1 H), 4.41 and 4.35 (d, J= 7.7 and 6.9, 1 H), 4.09-4.00 and 3.74-3.63 (m, 1 H), 3.21-3.12 and 3.06-2.97 (m, 1 H), 2.95-2.82 and 2.73-2.63 (m, 1 H), 2.09-1.73 (m, 2.5 H), 1.72-1.50 (m, 1 H), 1.65 (5, 3 H), 1.57 (5, 3 H), 1.50-1.39 (m, 0.5 H), 1.30-1.09 (m, 1 H), 0.97 and 0.95 (d, J= 6.6, 3 H), OH, NH not assigned.

[0248] 'H-NMR (600 MHz, DMSO-de, minor isomers): 5.14-5.04 (m, 1 H), 4.45 and 4.30 (d, J = 7.3, 1 H), 4.09-4.00 and 3.74-3.63 (m, 1 H), 3.21-3.12 and 3.06-2.97 (m, 1 H), 2.95- 2.82 and 2.73-2.63 (m, 1 H), 2.09-1.73 (m, 2.5 H), 1.72-1.50 (m, 1 H), 1.65 (5, 3 H), 1.57 (5, 3 H), 1.50-1.39 (m, 0.5 H), 1.30-1.09 (m, 1 H), 1.02 and 0.90 (d, J= 6.6, 3 H), OH, NH not assigned.

[0249] 13C-NMR (150.9 MHz, DMSO-d6, major isomers): 172.86 and 172.33, 130.72 and 130.68, 124.28 and 124.23, 76.79 and 75.94, 65.10 and 64.33, 38.36 and 36.74, 36.43 and 36.40, 34.68 and 34.29, 25.41, 24.76 and 24.72, 17.47 and 17.44, 17.01 and 16.70.

[0250] 13C-NMR (150.9 MHz, DMSO-d6, minor isomers): 172.86 and 172.31, 130.86 and 130.58, 124.40 and 124.10, 76.79 and 76.05, 65.10 and 64.33, 37.91 and 37.21, 36.60 and 36.28, 34.89 and 34.60, 25.41, 24.72 and 24.57, 17.44, 17.06 and 16.40.

[0251] Synthesis of ethyl (±)-(4R)-2-(undecan-2-yl)thiazolidine-4-carboxylate (Compound 4)

[0252] (±)-2 -Methylundecanal (2.79 g, 15.0 mmol) was added to a solution of ethyl L-cysteinate hydrochloride (5.68 g, 30.0 mmol) and TEA (4.6 mL, 33.0 mmol) in ethanol (100 mL). The mixture was heated under reflux (80°C) for 2 h. After cooling to room temperature, the solvent was removed under reduced pressure. Then demineralized water (100 mL) was added to the residue, and the mixture extracted with diethyl ether (2x 100 mL). The combined organic phases were washed with a saturated aqueous solution of NaCl (50 mL), dried (Na2SO4), filtered and concentrated to give a yellow oil, containing a solid, n- Hep tane was added, and the product filtered and concentrated. Column chromatography (SiCh. n- heptane / ethyl acetate 9:1) and drying under high vacuum gave 4.02 g (85%) of the target compound as a mixture of four diastereoisomers (ca. 37:37:14:12).

[0253] 'H-NMR (500 MHz, major isomers): 4.48 and 4.42 (d, J = 6.4 and 7.1, 1 H), 4.30-4.16 (m, 2 H), 3.84-3.76 (m, 1 H), 3.31-3.34 (m, 1 H), 2.75 (q, J= 9.9, 1 H), 2.25 (br. s, 1 H), 1.96- 1.79 (m, 1 H), 1.68-1.57 (m, 1 H), 1.44-1.18 (m, 18 H), 1.10 and 1.03 (d, J = 6.7, 3 H), 0.88 (t, J= 6.9, 3 H).

[0254] 'H-NMR (500 MHz, minor isomers): 4.55 and 4.51 (d, J= 7.4 and 7.7, 1 H), 4.30-4.16 (m, 2 H), 4.12-4.05 (m, 1 H), 3.22-3.14 (m, 1 H), 3.05-2.98 (m, 1 H), 2.25 (br. s, 1 H), 1.76- 1.57 (m, 1 H), 1.55-1.45 (m, 1 H), 1.44-1.18 (m, 18 H), 1.03 and 0.96 (d, J = 6.7, 3 H), 0.88 (t, J= 6.9, 3 H).

[0255] 13C-NMR (125.8 MHz, major isomers): 171.45 and 171.44, 77.15 and 77.13, 65.45, 61.54, 38.35 and 37.79, 37.56 and 37.37, 35.19 and 34.99, 31.91, 29.78 and 29.75, 29.65, 29.61 and 29.60, 29.33, 27.04 and 26.86, 22.69, 16.98 and 16.70, 14.17, 14.12.

[0256] 13C-NMR (125.8 MHz, minor isomers): 171.82, 75.98 and 75.85, 64.48 and 64.42, 61.46, 39.94 and 39.52, 37.32 and 37.17, 34.69 and 34.32, 31.91, 29.87 and 29.84, 29.65, 29.61 and 29.60, 29.33, 26.99 and 26.96, 22.69, 16.96 and 16.31, 14.17, 14.12.

[0257] Synthesis of (±)-(4R)-2-(undecan-2-yl)thiazolidine-4-carboxylic acid (Compound 5)

[0258] (±)-2 -Methylundecanal (9.31 g, 50.0 mmol) was added to a suspension of L-cysteine (6.12 g, 50.0 mmol) in ethanol (250 mL). The reaction mixture was heated under reflux for 24 h. When cooling to room temperature, the product crystallized. The reaction mixture was reheated to reflux and filtered at elevated temperature. The filtrate was cooled on an ice bath, and the crystallized product was filtered and washed with ice-cold ethanol (25 mL). Recrystallization of the filtrate (2x) afforded a total of 10.97 g (76%) of the target compound as a mixture of four diastereoisomers (ca. 29:27:25:19).

[0259] 'H-NMR (500 MHz, DMSO-d6): 4.44, 4.39, 4.34 and 4.28 (d, J = 7.4, 8.0, 7.1 and 7.7, 1 H), 4.07-4.01 and 3.72-3.66 (m, 1 H), 3.20-3.13, 3.05-2.97, 2.93-2.87 and 2.72-2.64 (m, 2 H), 1.90-1.73 (m, 0.5 H), 1.70-1.50 (m, 1 H), 1.47-1.04 (m, 17.5 H), 1.00, 0.95, 0.93 and 0.88 (d, J= 6.7, 3 H), 0.86 (t, J= 6.9, 3 H).

[0260] 13C-NMR (125.8 MHz, DMSO-d6): 172.87, 172.33 and 172.32, 76.94, 76.88, 76.17 and 76.11, 65.08, 64.33 and 64.30, 38.80, 38.37, 37.59 and 37.15, 36.59, 36.41 and 36.27, 34.71, 34.53, 34.43 and 34.09, 31.21, 29.25, 29.21, 29.17 and 29.10, 28.94, 28.91, 28.89 and 28.87, 28.62, 26.20, 26.15, 26.12 and 25.96, 22.01, 17.18, 17.16, 16.85 and 16.53, 13.86.

[0261] Synthesis of sodium (±)-(4R)-2-(undecan-2-yl)thiazolidine-4-carboxylate (Compound 6)

[0262] (±)-(47?)-2-(Undecan-2-yl)thiazolidine-4-carboxylic acid (Compound 5, 0.74 g, 1.7 mmol) was added to a solution of NaHCCh (0.15 g, 1.7 mmol) in water (50 mL). The mixture was sonicated for 1 h at ca. 25 °C. Filtration over a Buchner filter and lyophilization of the filtrate overnight afforded 0.66 g (quant.) of the target compound as a mixture of four diastereoisomers (ca. 48:25:16:11).

[0263] 'H-NMR (600 MHz, DMSO-d6): 4.44, 4.40, 4.33 and 4.27 (d, J = 8.5, 8.5, 6.2 and 6.9, 1 H), 3.58-3.32 and 3.31-3.24 (m, 3 H), 3.07-2.98 and 2.63-2.47 (m, 2 H), 1.84-1.69 (m, 0.5 H), 1.65-1.50 (m, 0.5 H), 1.49-1.10 (m, 15.5 H), 1.07-0.97 (m, 0.5 H), 1.00, 0.94, 0.91 and 0.83 (d, J= 6.6, 3 H), 0.86 (t, J= 6.7, 3 H).

[0264] 13C-NMR (150.9 MHz, DMSO-d6): 173.86, 173.73 and 173.71, 77.51, 77.46, 76.81 and 76.59, 68.80 and 67.29, 40.51, 40.27, 37.68 and 37.15, 38.66, 38.56, 38.11 and 37.92, 34.72, 34.67, 34.14 and 33.67, 31.20, 29.40, 29.28, 29.24 and 29.16, 29.01, 28.95, 28.91, 28.90 and 28.89, 28.62, 26.39, 26.35, 26.25 and 26.16, 22.01, 17.14, 17.12, 16.65 and

[0265] 16.51, 13.86.

[0266] Synthesis of ethyl (±)-(4R)-2-(2,4-dimethyl-3-cyclohexenyl)thiazolidine-4-carboxylate (Compound 7)

[0267] The compound was prepared as described in the general method using (±)-2,4-dimethyl-3- cyclohexene-l-carbaldehyde (Triplal®, mixture of two isomers, ca. 40:60, 2.12 g, 15.3 mmol) as the compound of formula (II). Column chromatography (SiCh. ^-heptane / ethyl acetate 9:1) gave 2.86 g (69%) of the target compound as a mixture of eight diastereoisomers (ca. 21:18:15:14:11 :9:7:5).

[0268] ‘H-NMR (500 MHz): 5.40-5.33 and 5.25-5.19 (m, 1 H), 4.85-4.79 and 4.79-4.66 and 4.55, 4.51 (d, J= 10.6) and 4.47-4.31 (m, 1 H), 4.31-4.15 (m, 2 H), 4.14-4.01 and 3.86-3.75 (m, 1 H), 3.34-3.16 and 3.09-2.93 and 2.82-2.72 (m, 2 H), 2.52-1.36 (m, 9 H), 1.34-1.25 (m, 3 H), 1.08-1.01 and 0.98-0.85 (m, 3 H), NH not assigned.

[0269] 13C-NMR (125.8 MHz): 171.85, 171.83, 171.79, 171.54, 171.51, 171.49, 171.47, 133.07, 133.02, 132.98, 132.95, 132.89, 132.86, 132.78, 127.42, 127.22, 127.00, 126.98, 126.41, 126.31, 126.06, 74.80, 73.98, 73.83, 73.55, 73.18, 72.58, 71.95, 65.60, 65.53, 65.38, 65.30, 64.48, 64.38, 64.19, 64.14, 61.55, 61.53, 61.47, 61.45, 45.70, 45.50, 44.98, 44.73,

[0270] 44.52, 44.30, 44.24, 37.64, 37.55, 37.49, 37.30, 37.25, 37.22, 37.19, 37.14, 34.62, 34.05,

[0271] 33.65, 33.54, 33.03, 31.97, 31.94, 31.75, 30.85, 30.79, 30.65, 30.58, 28.03, 28.01, 27.81,

[0272] 27.51, 23.58, 23.54, 23.51, 23.50, 23.40, 23.39, 23.37, 23.78, 23.06, 22.69, 22.49, 22.33,

[0273] 22.07, 21.78, 21.39, 21.29, 21.24, 21.16, 15.52, 15.42, 15.12, 14.93, 14.18, 14.16. Synthesis of ethyl (±)-(4R)-2-(3- and 4-(4-methyl-3-pentenyl)-3-cyclohexenyl)thiazolidine-4- carboxylate (Compound 8)

[0274] The compound was prepared as described in the general method using (±)-3- and 4-(4-methyl- 3 -pentenyl)-3 -cyclohexene- 1 -carbaldehyde (Empetal, ca. 31:69, 2.89 g) as the compound of formula (II). Column chromatography (SiCh. ^-heptane / ethyl acetate 9: 1, then 8:2) gave 4.27 g (80%) of the target compound as a mixture of eight isomers (ca. 24:23:12:11 :10:9:6:5), with four corresponding to the 3-isomer (ca. 11 :9:6:5, total 31%) and four corresponding to the 4- isomer (ca. 24:23:12:10, total 69%).

[0275] 'H-NMR (500 MHz, major isomers): 5.40-5.34 (m, 1 H), 5.12-5.05 (m, 1 H), 4.50-4.38 (m, 1 H), 4.30-4.17 (m, 2 H), 3.86-3.75 (m, 1 H), 3.32-3.26 (m, 1 H), 2.80-2.73 (m, 1 H), 2.45 (br. s, 1 H), 2.39-2.31 and 2.20-2.12 (m, 1 H), 2.12-1.75 (m, 9 H), 1.68 (5, 3 H), 1.60 (5, 3 H), 1.56-1.33 (m, 1 H), 1.30 (t, J= 7.1, 3 H).

[0276] 13C-NMR (125.8 MHz, major isomers): 171.44 and 171.38, 137.79 and 137.72, 131.44, 124.26 and 124.25, 119.09 and 119.07, 76.39 and 76.37, 65.55 and 65.41, 61.56, 39.95 and 39.45, 37.56 and 37.53, 37.37 and 37.34, 30.37 and 29.71, 28.01* and 27.99*, 27.47* and 27.01*, 26.44* and 26.41*, 25.71, 17.70, 14.17.

[0277] Synthesis of ethyl (±)-(4R)-2-(2-phenylpropyl)thiazolidine-4-carboxylate (Compound 9)

[0278] The compound was prepared as described in the general method using (±)-3 -phenylbutanal (Trifemal®, 91%, 2.77 g, 17.0 mmol) as the compound of formula (II). Column chromatography (SiCh. « -heptane / ethyl acetate 9:1, then 8:2) gave 3.09 g (65%) of the target compound as a mixture of four diastereoisomers (ca. 34:32:18:16).

[0279] ‘H-NMR (500 MHz, major isomers): 7.33-7.26 (m, 2 H), 7.25-7.16 (m, 3 H), 4.37 (t; J= 6.4, 0.5 H), 4.30-4.12 (m, 2.5 H), 3.73 and 3.68 (dd, J = 8.7, 7.4 and 9.0, 7.4, 1 H), 3.29-3.21 (m, 2 H), 3.09-2.78 (m, 1 H), 2.44-2.36 (m, 0.5 H), 2.23-1.78 (m, 1.5 H), 1.62 (br. s, 1 H), 1.34-1.22 (m, 6 H).

[0280] ‘H-NMR (500 MHz, minor isomers): 7.33-7.26 (m, 2 H), 7.25-7.16 (m, 3 H), 4.52 and 4.43 (dd, J= 8.3, 5.8 and 9.0, 5.8, 1 H), 4.30-4.12 (m, 2 H), 4.05 and 4.04 (t, J = 6.9, 1 H), 3.29-3.21 (m, 2 H), 3.09-2.78 (m, 1 H), 2.23-1.78 (m, 2 H), 1.62 (br. s, 1 H), 1.34-1.22 (m, 6 H).13C-NMR (125.8 MHz, major isomers): 171.38 and 171.27, 146.12 and 145.61, 128.53 and 128.49, 127.02 and 126.94, 126.43 and 126.33, 69.61 and 69.42, 65.29and 65.09, 61.56 and 61.55, 44.33 and 44.22, 39.26 and 38.59, 38.15 and 37.89, 22.95 and 22.31, 14.15.

[0281] 13C-NMR (125.8 MHz, minor isomers): 171.61 and 171.51, 146.30 and 145.97, 128.53 and 128.49, 127.16 and 127.08, 126.28 and 126.23, 68.44 and 68.00, 64.07 and 63.90, 61.53 and 61.50, 46.90 and 46.63, 38.23 and 38.17, 37.87 and 37.62, 22.45 and 22.28, 14.14.

[0282] Synthesis of ethyl (±)-(4R)-2-(2-((S)-4-methyl-3-cyclohexenyl)propyl)thiazolidine-4- carboxylate (Compound 10)

[0283] The compound was prepared as described in the general method using (7?)-3-((S)-4-methyl-3- cyclohexen-l-yl)butanal (Liminal®, 2.53 g) as the compound of formula (II). Column chromatography (SiCh. n -heptane / ethyl acetate 9:1, then 8:2) gave 3.73 g (84%) of the target compound as a mixture of four diastereoisomers (ca. 45:27:15:13).

[0284] 'H-NMR (500 MHz, major isomer): 5.36 (br. s, 1 H), 4.57 (br. s, 1 H), 4.31-4.17 (m, 2 H), 5.87-5.74 (m, 1 H), 3.35-3.21 (m, 1 H), 2.85 (q, J = 9.5, 1 H), 2.30-2.08 (br. m, 1 H), 2.08-1.61 (m, 7 H), 1.63 (5, 3 H), 1.60-1.38 (m, 2 H), 1.38-1.15 (m, 1 H), 1.30 (t, J = 7.2, 3 H), 0.93 ( , J = 6.7, 3 H).

[0285] 'H-NMR (500 MHz, second most abundant isomer): 5.36 (br. s, 1 H), 4.57 (br. s, 1 H), 4.31- 4.17 (m, 2 H), 5.87-5.74 (m, 1 H), 3.35-3.21 (m, 1 H), 2.85 (q, J= 9.5, 1 H), 2.30-2.08 (br. m, 1 H), 2.08-1.61 (m, 8 H), 1.63 (5, 3 H), 1.60-1.38 (m, 1 H), 1.38-1.15 (m, 1 H), 1.30 (t, J= 7.2, 3 H), 0.91 (d, J= 6.7, 3 H).

[0286] 'H-NMR (500 MHz, minor isomers): 5.36 (br. s, 1 H), 4.81-4.72 (m, 1 H), 4.31-4.17 (m, 2 H), 4.16-4.07 (m, 1 H), 3.35-3.21 (m, 1 H), 3.09-3.00 (m, 1 H), 2.30-2.08 (br. m, 1 H), 2.08-1.61 (m, 7.5 H), 1.63 (5, 3 H), 1.60-1.38 (m, 1.5 H), 1.38-1.15 (m, 1 H), 1.30 (t, J = 7.2, 3 H), 0.91 and 0.90 (d, J= 6.7, 3 H).

[0287] 13C-NMR (125.8 MHz, major isomer): 171.35, 134.00, 120.78, 70.37, 65.29, 61.57, 40.18, 38.99, 37.78, 36.71, 30.79, 29.03, 25.49, 23.45*, 16.30, 14.17.

[0288] 13C-NMR (125.8 MHz, second most abundant isomer): 171.72*, 134.07, 120.66, 69.45, 65.30, 61.58*, 40.64, 38.15, 37.99, 36.13, 30.93, 27.21, 26.92, 23.44*, 15.71, 14.17.

[0289] 13C-NMR (125.8 MHz, minor isomers): 171.39, 134.04 and 134.00, 120.91 and 120.75, 69.22 and 68.42, 64.16 and 63.95, 61.50, 42.52 and 42.40, 38.62 and 38.38, 37.66 and 37.38, 35.97 and 35.44, 30.90 and 30.82, 29.33 and 27.41, 26.81 and 25.02, 23.44, 15.86 and 15.67, 14.17.

[0290] Synthesis of ethyl (^)-(4R)-2-((Z)-3-nonenyl)thiazolidine-4-carboxylate (Compound 11)

[0291] The compound was prepared as described in the general method using (Z)-4-decenal (2.34 g) as the compound of formula (II). Column chromatography (SiCh. n-heptane / ethyl acetate 9:1) gave a total of 4.24 g (99%) of the target compound as a mixture of two diastereoisomers (ca. 61:39).

[0292] 'H-NMR (500 MHz, major isomer): 5.47-5.29 (m, 2 H), 4.57-4.47 (m, 1 H), 4.31-4.17 (m, 2 H), 3.85-3.75 (m, 1 H), 3.31 (dd, J = 10.3, 7.1, 1 H), 2.84 (dd, J = 10.3, 9.6, 1 H), 2.23 (q, J= 7.5, 2 H), 2.11-1.99 (m, 3 H), 1.93-1.78 (m, 1 H), 1.39-1.23 (m, 6 H), 1.30 (t, J = 7.1, 3 H), 0.89 (t, J = 6.9, 3 H), NH not assigned.

[0293] 'H-NMR (500 MHz, minor isomer): 5.47-5.29 (m, 2 H), 4.69 (t, J= 6.9, 1 H), 4.31-4.17 (m,

[0294] 2 H), 4.07 (t, J = 6.9, 1 H), 3.27 (dd, J = 10.6, 6.7, 1 H), 3.00 (dd, J = 10.6, 6.7, 1 H), 2.17 (q, J= 1A, 2 H), 2.11-1.99 (m, 2 H), 1.93-1.78 (m, 1 H), 1.69-1.59 (m, 1 H), 1.39- 1.23 (m, 6 H), 1.30 (t, J= 7.1, 3 H), 0.89 (t, J= 6.9, 3 H), NH not assigned.

[0295] 13C-NMR (125.8 MHz, major isomer): 171.34, 131.46, 127.85, 70.80, 65.42, 61.59, 38.01, 35.61, 31.51, 29.35, 27.22, 25.59, 22.58, 14.16, 14.08.

[0296] 13C-NMR (125.8 MHz, minor isomer): 171.65, 131.23, 128.05, 69.65, 64.05, 61.53, 38.22, 37.66, 31.51, 29.38, 27.24, 25.26, 22.58, 14.16, 14.08.

[0297] Synthesis of ethyl (±)-(4R)-2-((E)-3-nonenyl)thiazolidine-4-carboxylate (Compound 12)

[0298] The compound was prepared as described in the general method using (E)-4-decenal (2.39 g) as the compound of formula (II). Column chromatography (SiCh. n-heptane / ethyl acetate 9:1) gave a 2.28 g (53%) of the target compound as a mixture of two diastereoisomers (ca. 64:36). 'H-NMR (500 MHz, major isomer): 5.55-5.30 (m, 2 H), 4.55-4.45 (m, 1 H), 4.31-4.17 (m, 2

[0299] H), 3.84-3.75 (m, 1 H), 3.31 (dd, J= 10.3, 7.1, 1 H), 2.84 (t, J= 9.8, 1 H), 2.53-2.01 (m,

[0300] 3 H), 2.01-1.93 (m, 2 H), 1.93-1.78 (m, 1 H), 1.39-1.21 (m, 6 H), 1.30 (t, J= 7.2, 3 H), 0.88 (t, J= 7.1, 3 H), NH not assigned.

[0301] 'H-NMR (500 MHz, minor isomer): 5.55-5.30 (m, 2 H), 4.68 (t, J= 7.1, 1 H), 4.31-4.17 (m, 2 H), 4.07 (t, J = 6.9, 1 H), 3.26 (dd, J = 10.6, 7.1, 1 H), 2.99 (dd, J = 10.6, 7.1, 1 H), 2.53-2.01 (m, 2 H), 2.01-1.93 (m, 2 H), 1.93-1.78 (m, 1 H), 1.76-1.59 (m, 1 H), 1.39- 1.21 (m, 6 H), 1.30 (t, J = 7.2, 3 H), 0.88 (t, J = 7.1, 3 H), NH not assigned.

[0302] 13C-NMR (125.8 MHz, major isomer): 171.34, 131.89, 128.33, 70.70, 65.39, 61.57, 37.97, 35.60, 32.50, 31.39, 30.82, 29.14, 22.54, 14.16, 14.08.

[0303] 13C-NMR (125.8 MHz, minor isomer): 171.65, 131.69, 128.55, 69.53, 64.05, 61.52, 38.11,

[0304] 37.62, 32.54, 31.39, 30.48, 29.20, 22.54, 14.16, 14.08.

[0305] Synthesis of ethyl (±)-(4R)-2-((Z)-undec-3-en-l -yl)thiazolidine-4-carboxylate (Compound 13)

[0306] The compound was prepared as described in the general method using (Z)-4-dodecenal (2.77 g) as the compound of formula (II). Column chromatography (SiCh. « -heptane / ethyl acetate 95:5, then 9:1 and 8:2) gave a total of 3.66 g (78%) of the target compound as a mixture of two diastereoisomers (ca. 69:31).

[0307] 'H-NMR (600 MHz, major isomer): 5.51-5.30 (m, 2 H), 4.52 (dd, J = 6.9, 5.8, 1 H), 4.30- 4.18 (m, 2 H), 3.80 (dd, J= 9.6, 6.9, 1 H), 3.31 (dd, J= 10.4, 7.3, 1 H), 2.85 (t, J= 9.8, 1 H), 2.23 (q, J = 7.6, 2 H), 2.10-2.00 (m, 3 H), 1.92-1.78 (m, 1 H), 1.38-1.18 (m, 10 H), 1.30 (t, J= 7.1, 3 H), 0.88 (t, J= 6.9, 3 H), NH not assigned.

[0308] 'H-NMR (600 MHz, minor isomer): 5.51-5.30 (m, 2 H), 4.69 (t, J= 6.9, 1 H), 4.30-4.18 (m, 2 H), 4.07 (t, J = 6.9, 1 H), 3.27 (dd, J = 10.4, 6.9, 1 H), 3.00 (dd, J = 10.4, 6.9, 1 H),

[0309] 2.17 (q, J= 7.3, 2 H), 2.10-2.00 (m, 2 H), 1.92-1.78 (m, 1 H), 1.69-1.60 (m, 1 H), 1.38-

[0310] 1.18 (m, 10 H), 1.30 (t, J= lA, 3 H), 0.88 (t, J= 6.9, 3 H), NH not assigned.

[0311] 13C-NMR (150.9 MHz, major isomer): 171.33, 131.47, 127.84, 70.80, 65.42, 61.59, 38.00,

[0312] 35.62, 31.87, 29.69, 29.28, 29.23, 27.27, 25.59, 22.68, 14.16, 14.12.

[0313] 13C-NMR (150.9 MHz, minor isomer): 171.64, 131.24, 128.04, 69.65, 64.05, 61.53, 38.22, 37.66, 31.87, 29.72, 29.28, 29.23, 27.28, 25.27, 22.68, 14.16, 14.12.

[0314] Synthesis of methyl (±)-(4R)-2-(2-(4,4-dimethyl-l -cyclohexenyl)ethyl)thiazolidine-4- carboxylate (Compound 14)

[0315] 3 -(4, 4-Dimethyl cyclohex- l-en-l-yl)propanal (Tillenal®, 2.96 g, 17.5 mmol) was added to a solution of methyl L-cysteinate hydrochloride (2.89 g, 16.5 mmol) and TEA (2.5 mL, 18.0 mmol) in methanol (50 mL). The mixture was heated under reflux (60°C) for 2 h. After cooling to room temperature, the solvent was removed under reduced pressure. Then ethyl acetate (100 mL) was added, and the solution washed with a saturated aqueous solution of NaHCCh (50 mL). The aqueous phase was re-extracted with ethyl acetate (100 mL) and the combined organic phases washed with a saturated aqueous solution of NaCl (50 mL), dried (Na2SO4), filtered and concentrated. Column chromatography (SiCh. n -heptane / ethyl acetate 9:1 and 8:2) gave a total of 4.09 g (96%) of the target compound as a mixture of two diastereoisomers (ca. 65:35).

[0316] 'H-NMR (600 MHz, major isomer): 5.39-5.32 (m, 1 H), 4.51-4.44 (m, 1 H), 3.86-3.77 (m, 1 H), 3.79 (5, 3 H), 3.30 (dd, J = 10.4, 6.9, 1 H), 2.84 (t, J = 9.8, 1 H), 2.24 (br. m, 1 H), 2.17-2.05 (m, 3 H), 2.00-1.81 (m, 3 H), 1.80-1.74 (m, 2 H), 1.39-1.32 (m, 2 H), 0.88 (5, 6 H).

[0317] 'H-NMR (600 MHz, minor isomer): 5.39-5.32 (m, 1 H), 4.63 (t, J= 6.9, 1 H), 4.11 (t, J= 6.6, 1 H), 3.77 (5, 3 H), 3.25 (dd, J= 10.4, 6.9, 1 H), 3.02 (dd, J= 10.8, 6.6, 1 H), 2.44 (br. s, 1 H), 2.17-2.05 (m, 2 H), 2.00-1.81 (m, 3 H), 1.80-1.74 (m, 2 H), 1.74-1.64 (m, 1 H), 1.39-1.32 (m, 2 H), 0.89 (5, 6 H).

[0318] 13C-NMR (150.9 MHz, major isomer): 171.75, 134.83, 120.97, 70.91, 65.26, 52.48, 39.24, 37.88, 35.65, 35.60, 33.89, 28.46, 28.30, 28.11, 26.01.

[0319] 13C-NMR (150.9 MHz, minor isomer): 172.10, 134.98, 120.78, 69.75, 63.99, 52.49, 39.27, 37.51, 36.33, 35.68, 35.30, 28.46, 28.30, 28.09, 26.14.

[0320] Synthesis of ethyl (±)-(4R)-2-(2-(4,4-dimethylcyclohex-l -en-1 -yl)ethyl)thiazolidine-4- carboxylate (Compound 15)

[0321] Tillenal® (12.94 g, 75.0 mmol) was added to a solution of ethyl L-cysteinate hydrochloride (15.63 g, 82.5 mmol) and TEA (12.5 mL, 90.0 mmol) in ethanol (250 mL). The mixture was heated under reflux (80°C) for 2 h, left cooling to room temperature and stirred overnight. The solvent was removed under reduced pressure. Then ethyl acetate (150 mL) was added, and the organic layer washed with a saturated aqueous solution of NaHCCh (100 mL). The aqueous phase was re-extracted with ethyl acetate (150 mL) and the combined organic phases washed with a saturated aqueous solution of NaCl (100 mL), dried (Na2SO4), filtered and concentrated. Column chromatography of 6.00 g (SiCh. n -heptane / ethyl acetate 9:1 and 8:2) gave a total of 5.26 g (91%) of the target compound as a mixture of two diastereoisomers (ca. 64:36). 'H-NMR (500 MHz, major isomer): 5.40-5.32 (m, 1 H), 4.48 (dd, J = 7.7, 4.5, 1 H), 4.31- 4.16 (m, 2 H), 3.80 (dd, J= 9.3, 7.1, 1 H), 3.30 (dd, J= 10.3, 7.1, 1 H), 2.83 (t, J= 9.8, 1 H), 2.24 (br. s, 1 H), 2.18-2.09 (m, 3 H), 2.01-1.81 (m, 3 H), 1.80-1.73 (m, 2 H), 1.39-

[0322] 1.23 (m, 2 H), 1.30 (1, 7= 7.2, 3 H), 0.88 (5, 6 H).

[0323] 'H-NMR (500 MHz, minor isomer): 5.40-5.32 (m, 1 H), 4.65 (t, J= 6.9, 1 H), 4.31-4.16 (m, 2 H), 4.07 (t, J = 6.9, 1 H), 3.26 (dd, J = 10.6, 6.7, 1 H), 2.99 (dd, J = 10.6, 7.1, 1 H),

[0324] 2.24 (br. s, 1 H), 2.18-2.09 (m, 1 H), 2.08 (t, J = 7.7, 1 H), 2.01-1.81 (m, 3 H), 1.80-1.73 (m, 2 H), 1.73-1.64 (m, 1 H), 1.39-1.23 (m, 2 H), 1.30 (t, J= 7.2, 3 H), 0.89 (5, 6 H).

[0325] 13C-NMR (125.8 MHz, major isomer): 171.30, 134.84, 120.93, 70.96, 65.40, 61.53, 39.24, 37.93, 35.66, 35.62, 33.91, 28.46, 28.31, 28.11, 26.02, 14.17.

[0326] 13C-NMR (125.8 MHz, minor isomer): 171.61, 135.01, 120.72, 69.79, 64.06, 61.48, 39.27, 37.62, 36.49, 35.68, 35.28, 28.46, 28.29, 28.11, 26.15, 14.17.

[0327] Synthesis of ethyl (±)-(4R)-2-(4-methoxyphenyl)thiazolidine-4-carboxylate (Compound 16)

[0328] The compound was prepared as described in the general method using 4- methoxybenzaldehyde (Anisaldehyde, 2.04 g) as the compound of formula (II) and with heating under reflux (80°C) for 6 h. Column chromatography (SiCh. ^-heptane / ethyl acetate 9:1, then 8:2) gave 3.40 g (83%) of the target compound as a mixture of two diastereoisomers (ca. 68:32).

[0329] 'H-NMR (500 MHz, major isomer): 7.49-7.43 (m, 2 H), 6.93-6.86 (m, 2 H), 5.53 (br. d, J = 11.2, 1 H), 4.32-4.16 (m, 2 H), 4.00-3.90 (m, 1 H), 3.81 (5, 3 H), 3.46 (dd, J = 10.3, 7.1, 1 H), 3.11 (dd, J= 10.3, 9.0, 1 H), 2.69-2.53 (br. m, 1 H), 1.31 (t, J= 7.2, 3 H).

[0330] 'H-NMR (500 MHz, minor isomer): 7.44-7.39 (m, 2 H), 6.88-6.83 (m, 2 H), 5.78 (br. s, 1 H), 4.32-4.16 (m, 3 H), 3.79 (5, 3 H), 3.40 (dd, J = 10.6, 7.4, 1 H), 3.21 (dd, J = 10.6, 5.8, 1 H), 2.88-2.70 (br. m, 1 H), 1.31 (t, J= 7.2, 3 H).

[0331] 13C-NMR (125.8 MHz, major isomer): 171.24, 159.86, 130.16, 128.73, 114.03, 72.38, 65.64, 61.69, 55.34, 39.35, 14.18.

[0332] 13C-NMR (125.8 MHz, minor isomer): 171.83, 159.29, 133.12, 128.25, 113.76, 70.62, 64.31,

[0333] 61.58, 55.32, 38.15, 14.18.

[0334] Synthesis of ethyl (f)f4R)-2-nonylthiazohdine-4-carboxylate (Compound 17) The compound was prepared as described in the general method using decanal (2.49 g) as the compound of formula (II). A precipitate was formed. The product was taken up in a mixture of ethyl acetate and ethanol and re-concentrated. It was then taken up in acetone (30 mL) and heated under reflux for 15 min. After cooling on an ice bath, the suspension was filtered, washed with a minimum of ice-cold acetone, and the filtrate was concentrated. Column chromatography (SiCh. « -heptane / ethyl acetate 9:1, then 8:2) gave a total of 2.81 g (65%) of the target compound as a mixture of two diastereoisomers (ca. 70:30), together with small amounts of impurities.

[0335] 'H-NMR (500 MHz, major isomer): 4.51 (dd, J = 7.4, 5.8, 1 H), 4.32-4.17 (m, 2 H), 3.82 (dd, J = 9.3, 7.1, 1 H), 3.31 (dd, J= 10.3, 7.1, 1 H), 2.84 (t, J= 9.8, 1 H), 2.04-1.94 (m, 1 H), 1.81-1.70 (m, 1 H), 1.55-1.18 (m, 17 H), 0.88 (t, J = 6.9, 3 H), NH not assigned.

[0336] 'H-NMR (500 MHz, minor isomer): 4.66 (dd, J = 7.4, 6.4, 1 H), 4.32-4.17 (m, 2 H), 4.10 (t, J = 6.7, 1 H), 3.26 (dd, J = 10.6, 7.1, 1 H), 3.03 (dd, J = 10.6, 6.4, 1 H), 1.89-1.79 (m, 1 H), 1.67-1.55 (m, 1 H), 1.55-1.18 (m, 17 H), 0.88 (t, J= 6.9, 3 H), NH not assigned.

[0337] 13C-NMR (125.8 MHz, major isomer): 171.36, 71.23, 65.36, 61.58, 37.87, 35.69, 31.88, 29.49, 29.46, 29.43, 29.29, 27.91, 22.68, 14.16, 14.11.

[0338] 13C-NMR (125.8 MHz, minor isomer): 171.68, 70.21, 64.08, 61.51, 38.15, 37.50, 31.88, 29.51* (2 C), 29.33*, 29.29, 27.58, 22.68, 14.16, 14.11.

[0339] Synthesis of ethyl (±)-(4R)-2-(4,8-dimethylnon-3-en-l -yl)thiazolidine-4-carboxylate

[0340] (Compound 18)

[0341] The compound was prepared as described in the general method using (A7Z)-5.9-dimethyldec- 4-enal (ca. 57:43, 2.78 g) as the compound of formula (II). Column chromatography (SiCh, n- heptane / ethyl acetate 9:1, then 8:2) gave 3.66 g (78%) of the target compound as a mixture of four isomers (ca. 39:30:18:13), with two corresponding to the (A’)-isomer (ca. 39:18, total 57%) and two corresponding to the (Z)-isomer (ca. 30:13, total 43%).

[0342] 'H-NMR (500 MHz, major isomers): 5.15-5.07 (m, 1 H), 4.56-4.47 (m, 1 H), 4.32-4.17 (m, 2 H), 3.85-3.75 (m, 1 H), 3.31 (dd, J= 10.3, 6.7, 1 H), 2.84 (t, J= 9.8, 1 H), 2.55-1.91 (m, 6 H), 1.91-1.75 (m, 1 H), 1.70-1.58 (m, 3 H), 1.58-1.47 (m, 1 H), 1.42-1.31 (m, 2 H), 1.30 (t, J= 7.0, 3 H), 1.19-1.09 (m, 2 H), 0.87 (d, J = 6.7, 6 H).

[0343] 'H-NMR (500 MHz, minor isomers): 5.15-5.07 (m, 1 H), 4.68 (t, J= 6.9, 1 H), 4.32-4.17 (m, 2 H), 4.07 (t, J= 6.7 and 6.9, 1 H), 3.26 (dd, J= 10.6, 7.1, 1 H), 3.00 (dd, J= 10.6, 6.7, 1 H), 2.55-1.91 (m, 5 H), 1.91-1.75 (m, 1 H), 1.70-1.58 (m, 4 H), 1.58-1.47 (m, 1 H), 1.42-1.31 (m, 2 H), 1.30 (t, J= 7.2, 3 H), 1.19-1.09 (m, 2 H), 0.87 (d, J = 6.7, 6 H).

[0344] 13C-NMR (125.8 MHz, major isomers): 171.34, 137.08 and 136.88, 123.33 and 122.56, 70.92 and 70.88, 65.43, 61.55, 39.88 and 31.98, 38.86 and 38.61, 38.01 and 38.00, 35.95 and 35.76, 27.93 and 27.88, 26.26 and 26.13, 25.78 and 25.64, 23.40 and 15.99, 22.65, 14.17.

[0345] 13C-NMR (125.8 MHz, minor isomers): 171.67, 136.81 and 136.64, 123.49 and 122.73, 69.75 and 69.74, 64.07 and 64.06, 61.50, 39.90 and 31.99, 38.87 and 38.61, 38.56 and 38.30, 37.65, 27.93 and 27.88, 25.92 and 25.79, 25.82 and 25.70, 23.40 and 15.99, 22.65, 14.17.

[0346] Synthesis of ethyl (±)-(4R)-2-(6-hydroxy-2,6-dimethylheptyl)thiazolidine-4-carboxylate (Compound 19)

[0347] The compound was prepared as described in the general method using (±)-7-hydroxy-3,7- dimethyloctanal (2.60 g) as the compound of formula (II) to give 4.66 g of the target compound as a mixture of four diastereoisomers (ca. 38:35:15:12).

[0348] 'H-NMR (500 MHz, major isomers): 4.62-4.53 (m, 1 H), 4.32-4.17 (m, 2 H), 3.84-3.76 (m, 1 H), 3.35-3.27 (m, 1 H), 2.85 and 2.84 (t, J = 9.8, 1 H), 2.17 (br. s, 1 H), 2.00-1.55 (m, 2 H), 1.52-1.11 (m, 6 H), 1.30 (t, J = 7.2, 3 H), 1.21 (5, 6 H), 0.96 and 0.95 (d, J= 6.4, 3 H), OH and NH not assigned.

[0349] 'H-NMR (500 MHz, minor isomers): 4.80-4.73 (m, 1 H), 4.32-4.17 (m, 2 H), 4.16-4.08 (m, 1 H), 3.30-3.21 (m, 1 H), 3.06 and 3.04 (t, J = 6.7, 1 H), 2.17 (br. s, 1 H), 2.00-1.55 (m, 1.5 H), 1.52-1.11 (m, 6.5 H), 1.30 (t, J= 7.1, 3 H), 1.21 (5, 6 H), 0.95 and 0.93 (d, J = 6.4, 3 H), OH and NH not assigned.

[0350] 13C-NMR (125.8 MHz, major isomers): 171.39 and 171.36, 71.01 and 70.99, 69.82 and 69.34, 65.36 and 65.32, 61.60 and 61.59, 44.07 and 44.05, 43.28 and 43.17, 38.10, 37.87, 37.84 and 37.17, 32.37 and 31.92, 29.35, 29.21, 21.56 and 21.46, 19.79 and 19.55, 14.17.

[0351] 13C-NMR (125.8 MHz, minor isomers): 171.72, 71.01 and 70.99, 68.76 and 68.20, 64.12 and 64.00, 61.51, 45.43 and 45.14, 44.10 and 44.08, 37.68, 37.64, 37.46 and 37.20, 31.63 and 31.42, 29.38, 29.21, 21.52 and 21.50, 19.54 and 19.44, 14.17.

[0352] Synthesis of ethyl (^)-(4R)-2-((E)-3-methyl-4-(4-methylphenyl)but-3-en-l-yl)thiazolidine-4- carboxylate (Compound 20) The compound was prepared as described in the general method using (E)-4-methyl-5-(4- methylphenyl)pent-4-enal (Mimosal®, 2.94 g) as the compound of formula (II) to give 5.06 g (quant.) of the target compound as a mixture of two diastereoisomers (ca.58:42).

[0353] 'H-NMR (500 MHz, major isomer): 7.15-7.09 (m, 4 H), 6.29 (5, 1 H), 4.53 dd, J= 7.1, 5.4, 1 H), 4.31-4.17 (m, 2 H), 3.81 (dd, J = 9.3, 7.1, 1 H), 3.35-3.25 (m, 1 H), 2.86 (t, J= 9.8, 1 H), 2.41-2.15 (m, 4 H), 2.33 (5, 3 H), 2.09-1.93 (m, 1 H), 1.87 (d, J = 1.0, 3 H), 1.30 (t, J = 7.2, 3 H).

[0354] 'H-NMR (500 MHz, minor isomer): 7.15-7.09 (m, 4 H), 6.27 (5, 1 H), 4.71 (t, J = 6.9, 1 H),

[0355] 4.31-4.17 (m, 2 H), .4.09 (t, J= 6.9, 1 H), 3.35-3.25 (m, 1 H), 3.00 (dd, J= 10.6, 7.1, 1 H), 2.41-2.15 (m, 3 H), 2.33 (5, 3 H), 2.09-1.93 (m, 1 H), 1.91-1.75 (m, 1 H), 1.85 (d, J = 1.0, 3 H), 1.30 (t, J= 7.2, 3 H).

[0356] 13C-NMR (125.8 MHz, major isomer): 171.33, 136.64, 135.63, 135.35, 128.76, 128.74, 125.67, 70.77, 65.40, 61.61, 38.79, 38.03, 34.12, 21.14, 17.78, 14.18.

[0357] 13C-NMR (125.8 MHz, minor isomer): 171.62, 136.97, 135.55, 135.44, 128.74, 128.71, 125.48, 69.64, 64.07, 61.57, 38.45, 37.72, 36.76, 21.14, 17.90, 14.18.

[0358] Synthesis of ethyl (±)-(4R)-2-(2-(l,l- and 3,3-dimethyl-2,3-dihydro-lH-inden-5- and 4- yl)ethyl)thiazolidine-4-carboxylate (Compound 21)

[0359] The compound was prepared as described in the general method using 3-(l,l- and 3,3- dimethyl-2,3-dihydro-lH-inden-4- and 5-yl)propanal (Hivemal® Neo, mixture of three isomers, ca. 49:41:10, 3.08 g) as the compound of formula (II) to give 5.35 g (quant.) of the target compound as a mixture of six isomers (ca. 27:23:22:19:5:4).

[0360] 'H-NMR (500 MHz, major isomers): 7.16-6.93 (m, 3 H), 4.72-4.65 and 4.55-4.47 (m, 1 H),

[0361] 4.31-4.16 (m, 2 H), 4.15-4.05 and 3.84-3.76 (m, 1 H), 3.36-3.25 (m, 1 H), 3.04-2.96 (m, 0.5 H), 2.90-2.67 (m, 4.5 H), 2.37-2.01 (m, 2.5 H), 1.95-1.85 (m, 0.5 H), 1.91 (dt, J = 7.2, 1.6, 2 H), 1.33-1.21 (m, 9 H).

[0362] 13C-NMR (125.8 MHz, major isomers): 171.64, 171.62 and 171.34, 152.92, 152.88, 150.51, 150.35, 143.13, 143.08, 140.64 and 140.47, 139.32, 139.09, 139.05 and 138.83, 126.61, 126.50, 126.46 and 126.37, 124.59, 124.47, 124.37 and 124.34, 122.07, 121.98, 121.90 and 121.86, 70.63, 70.57, 69.49 and 69.41, 65.42, 64.10 and 64.09, 61.61 and 61.56, 43.88, 43.87, 43.63 and 43.62, 41.62 and 41.55, 40.33, 40.17, 37.68 and 37.57, 38.03, 38.02 and 37.75, 34.11, 33.91, 33.73 and 33.52, 29.99, 29.69 and 29.68, 28.66 and 28.61,

[0363] 14.18.

[0364] Synthesis of (^)-(4R)-2-benzylthiazolidine-4-carboxylic acid (Compound 22)

[0365] 2-Phenylacetaldehyde (4.96 g, 41.3 mmol) was added to a suspension of L-cysteine (5.00 g, 41.3 mmol) in ethanol (100 mL). After heating under reflux for 15 min, more ethanol (100 mL) was added. The reaction mixture was heated under reflux for 3 h, then left cooling to room temperature and filtered through sintered glass. The solid was rinsed with ethanol (2x, 10 mL) and dried under vacuum in a desiccator to give 7.65 g (83%) of the target compound as a mixture of two diastereoisomers (ca. 76:24).

[0366] 'H-NMR (500 MHz, DMSO-de, major isomer): 7.32-7.17 (m, 5 H), 4.81 (t, J = 7.1, 1 H), 4.14 (dd, J = 6.7, 5.4, 1 H), 3.14 (dd, J= 10.3, 6.7, 1 H), 3.10 (dd, J = 13.8, 6.7, 1 H), 2.92 (dd, J= 9.9, 5.4, 1 H), 2.83 dd, J= 13.8, 7.4, 1 H), OH, NH not assigned.

[0367] 'H-NMR (500 MHz, DMSO-de, minor isomer): 7.32-7.17 (m, 5 H), 4.65 (dd, J= lA, 6.4, 1 H), 3.72 (dd, J= 9.0, 6.7, 1 H), 3.24 (dd, J= 13.8, 6.4, 1 H), 3.18 (dd, J= 9.9, 7.1, 1 H), 2.99 (dd, J= 13.5, 7.1, 1 H), 2.78 (dd, J= 9.9, 9.3, 1 H), OH, NH not assigned.

[0368] 13C-NMR (125.8 MHz, DMSO-de, major isomer): 172.74, 138.98, 129.01, 128.01, 126.15, 71.24, 64.06, 42.76, 37.01.

[0369] 13C-NMR (125.8 MHz, DMSO-de, minor isomer): 172.15, 138.72, 128.83, 128.08, 126.29, 71.80, 65.20, 40.56, 37.25.

[0370] Synthesis of ethyl (±)-(4R)-2-methyl-2-(2-(2,6,6-trimethylcyclohex-l-en-l- yl)ethyl)thiazolidine-4-carboxylate (Compound 23)

[0371] The compound was prepared as described in the general method using 4-(2,6,6- trimethylcyclohex-l-en-l-yl)butan-2-one (Dihydro-beta-ionone, 2.34 g) as the compound of formula (II) and with heating under reflux (80°C) for 24 h. Repetitive column chromatography (SiO2, n -heptane / ethyl acetate 9:1 and 95:5) gave 2.73 g (56%) of the target compound as a mixture of two diastereoisomers (ca. 50:50).

[0372] 'H-NMR (500 MHz): 4.31-4.19 (m, 2 H), 4.13-3.97 (m, 1 H), 3.40 and 3.36 (dd, J= 10.4, 6.8 and 10.5, 7.0, 1 H), 3.00 and 2.92 (dd, J= 10.6, 9.0 and 10.5, 9.9, 1 H), 2.62-2.44 (m, 1 H), 2.29 (dt, J = 13.0, 4.4, 0.5 H), 2.18-2.05 (m, 1.5 H), 2.01 (dt, J = 13.2, 4.3, 0.5 H), 1.95-1.85 (m, 2.5 H), 1.83-1.68 (m, 1 H), 1.69 and 1.63 (5, 3 H), 1.63-1.49 (m, 2 H), 1.59 and 1.54 (5, 3 H), 1.45-1.37 (m, 2 H), 1.31 (t, J= 7.1, 3 H), 1.02 and 0.98 (d, J= 3.9 and 2.6, 6 H).

[0373] 13C-NMR (125.8 MHz): 171.79 and 171.61, 136.28 and 135.95, 127.80 and 127.29, 80.16 and 80.14, 64.53 and 64.07, 61.59 and 61.58, 44.08 and 43.06, 39.85 and 39.83, 39.71 and 39.23, 35.13 and 35.11, 32.79 and 32.75, 30.38 and 27.29, 28.69, 28.65 (2 C) and 28.58, 25.12 and 24.69, 19.90 and 19.79, 19.51 and 19.48, 14.17.

[0374] Synthesis of ethyl (±)-(4R)-2-(4-hydroxyphenethyl)-2-methylthiazolidine-4-carboxylate (Compound 24)

[0375] The compound was prepared as described in the general method using 4-(4-hydroxyphenyl)- 2-butanone (Raspberry ketone, 2.51 g, 15.3 mmol) as the compound of formula (II) and with heating under reflux (80°C) for 7 h. Column chromatography (SiCh. n-heptane / ethyl acetate 9:1, then 8:2) gave 2.00 g (44%) of the target compound as a mixture of two diastereoisomers (ca. 52:48).

[0376] 'H-NMR (500 MHz): 7.08-6.99 (m, 2 H), 6.78-6.71 (m, 2 H), 4.30-4.18 (m, 2 H), 4.11 and 4.05 (dd, J = 9.3, 7.1 and 9.0, 7.1, 1 H), 3.43 and 3.39 dd, J= 10.6, 7.1, 1 H), 3.02 and 2.95 (dd, J= 10.6, 9.0 and 10.6, 9.3, 1 H), 2.87-2.78 (m, 1 H), 2.75-2.58 (m, 1 H), 2.25- 2.07 (m, 1 H), 2.04-1.90 (m, 1 H), 1.71 and 1.57 (5, 3 H), 1.30 and 1.26 (t, J= 7.1, 3 H), OH and NH not assigned.

[0377] 13C-NMR (125.8 MHz): 171.77 and 171.62, 154.14 and 153.93, 133.75 and 133.17, 129.39 and 129.34, 115.42 and 115.30, 79.47 and 79.47, 64.45 and 64.08, 61.79 and 61.76, 46.36 and 45.06, 39.63 and 39.21, 31.56 and 31.16, 30.59 and 27.78, 14.14.

[0378] Synthesis of ethyl (±)-(3R)-6-pentyl-l-thia-4-azaspiro[4.4]nonane-3-carboxylate (Compound 25)

[0379] The compound was prepared as described in the general method using (±)-2- pentylcyclopentan-l-one (Delphone, 2.34 g) as the compound of formula (II) and with heating under reflux (80°C) for 24 h. Column chromatography (SiO2, n -heptane / ethyl acetate 95:5, then 8:2) gave 1.37 g (34%) of the target compound as a mixture of four diastereoisomers (ca. 38:35:17:10). 'H-NMR (500 MHz, major isomers): 4.31-4.17 (m, 2 H), 3.96-3.85 (m, 1 H), 3.38-3.29 (m, 1 H), 2.83 and 2.79 (dd, J= 10.6, 9.6 and t, J= 9.9, 1 H), 2.55 and 2.41 (br. s, 1 H), 2.16- 1.58 (m, 6 H), 1.58-1.00 (m, 12 H), 0.93-0.84 (m, 3 H).

[0380] 'H-NMR (500 MHz, minor isomers): 4.31-4.17 (m, 2 H), 4.01-3.85 (m, 1 H), 3.38-3.22 (m, 1 H), 3.00 and 2.94 (dd, J= 10.3, 8.3 and 10.3, 9.3, 1 H), 2.55 and 2.41 (br. s, 1 H), 2.26- 1.58 (m, 7 H), 1.58-1.00 (m, 11 H), 0.93-0.84 (m, 3 H).

[0381] 13C-NMR (125.8 MHz, major isomers): 171.72 and 171.71, 90.19 and 86.89, 64.03 and 64.02, 61.55 and 61.51, 47.99 and 47.35, 43.78 and 43.34, 39.13 and 38.38, 32.09 and 32.04, 29.91 and 29.80, 28.30, 28.07, 22.65 and 22.61, 21.67 and 20.91, 14.17, 14.07.

[0382] 13C-NMR (125.8 MHz, minor isomers): 171.93 and 171.78, 89.69 and 87.80, 65.61 and 64.55, 61.55 and 61.53, 52.59 and 50.53, 41.20 and 40.88, 39.39 and 38.74, 32.19 and 32.17, 29.39 and 29.35, 28.20, 28.05, 22.69, 21.11 and 20.97, 14.17, 14.10.

[0383] Synthesis of ethyl (±)-(4'R)-7-methyl-2H, 4H-spiro[benzo[b ][1, 4 ]dioxepine-3, 2 '-thiazolidine ]- 4'-carboxylate (Compound 26)

[0384] The compound was prepared as described in the general method using 7-methyl-2H- benzo[b][l,4]dioxepin-3(4H)-one (Calone®, 2.67 g) as the compound of formula (II) to give 4.87 g (quant.) of the target compound as a mixture of two diastereoisomers (ca. 50:50).

[0385] 'H-NMR (500 MHz): 6.85 and 6.83 (d, J = 5.4, 1 H), 6.77 and 6.76 (d, J = 7.7, 1 H), 6.74- 6.68 (m, 1 H), 4.49 and 4.47 (d, J= 10.3, 1 H), 4.31-4.19 (m, 3 H), 4.19 and 4.17 (d, J = 3.5 and 3.2, 1 H), 4.08-3.98 (m, 2 H), 3.32 and 3.30 (d, J= 5.8, 1 H), 2.97-2.90 (m, 1 H), 2.24 (5, 3 H), 1.31 t, J = 7.2, 3 H), NH not assigned.

[0386] 13C-NMR (125.8 MHz): 170.74, 149.60 and 149.50, 147.74 and 147.63, 133.41 and 133.11, 124.09 and 123.79, 121.25 and 121.23, 120.53 and 120.51, 79.88 and 79. 83, 78.27 and 78.12, 76.81 and 76.62, 63.79 and 63.78, 61.88, 37.63 and 37.62, 20.56 and 20.54, 14.15.

[0387] Synthesis of oxybis(ethane-2,l-diyl) (±)-(4R,4'R)-bis(2-((Z)-non-3-en-l-yl)thiazolidine-4- carboxylate) (Compound 27)

[0388] First step. Following a literature procedure for the synthesis of a similar compound (see: S. Pal et al. Macromolecules, 2022, Vol. 55, pages 2854-2860) N,N'-dicyclohexylcarbodiimide (2.40 g, 12.0 mmol) and N,N-dimethyl-4-aminopyridine (0.24 g, 2.0 mmol) were added in small portions to a stirred solution of 2-(2-hydroxyethoxy)ethanol (0.11 g, 1.0 mmol) and N- (tert-butoxycarbonyl)-S-trityl-L-cysteine (4.60 g, 10.0 mmol) in dichloromethane (20 mL), which was cooled on an ice bath at 0°C. After removing the ice bath, the reaction mixture was left stirring at room temperature for 5 days. The suspension was filtered, washed with dichloromethane (2x 30 mL) and the filtrate carefully concentrated to minimize foaming. Drying under vacuum afforded 5.32 g of the crude product. Column chromatography (SiCh. w-heptane / ethyl acetate 8:2, then 7:3) yielded 1.08 g (quant.) of oxybis(ethane-2,l-diyl) (2A’.2'A’)-bis(2-((tert-butoxycarbonyl)amino)-3 -(trityl thio)propanoate). still containing some n- heptane.

[0389] 'H-NMR (500 MHz): 7.41-7.35 (m, 12 H), 7.30-7.24 (m, 12 H), 7.23-7.18 (m, 6 H), 5.06 (br. d, J= 7.4, 2 H), 4.32-4.24 (m, 2 H), 4.24-4.13 (m, 4 H), 3.58 (t, J = 4.8, 4 H), 2.67-2.53 (m, 4 H), 1.43 (5, 18 H).

[0390] 13C-NMR (125.8 MHz): 170.76, 154.98, 144.31, 129.50, 128.01, 126.88, 79.99, 68.81, 66.82, 64.41, 52.50, 34.19, 28.32.

[0391] Second step. The tert-butoxycarbonyl- and tritylthio-protecting groups were removed according to a literature procedure (M. Maue et al. Synthesis, 2008, pages 2247-2256). Oxybis(ethane-2,l-diyl) (2A’.2'A’)-bis(2-((tert-butoxycarbonyl)amino)-3-(tritylthio)propanoate) (1.00 g, 1.0 mmol) was added in small portions during 15 min to a solution of trifluoro acetic acid (TFA, 20 mL) and triisopropylsilane (0.42 pL) in dichloromethane (20 mL). During the addition, the solution turned yellow and then discolored again. The reaction mixture was stirred at room temperature for 17 h. Then the dichloromethane and the TFA were distilled off at room temperature under reduced pressure (40 mbar, then 12 mbar). The temperature dropped to -24°C. After warming to room temperature, toluene (20 mL) was added, which then was distilled off under reduced pressure (ca. 2.5 mbar). This procedure was repeated twice (2x 20 mL) to finally give an off-white solid.

[0392] Third step. The solid was taken up in tetrahydrofuran (25 mL). Then TEA (20 drops) and (Z)- 4-decenal (0.78 g, 5.0 mmol) were added, and the reaction mixture was stirred under reflux for 4 h. After cooling to room temperature, the mixture was concentrated under reduced pressure. Column chromatography (SiCh. ^-heptane / ethyl acetate 9:1, then 8:2, then 7:3, then pure ethyl acetate) afforded 0.26 g (44%) of the target compound as a mixture of two pairs of diastereoisomers (ca. 55:45). 'H-NMR (600 MHz, DMSO-d6, major isomers): 5.42-5.28 (m, 4 H), 4.55 t, J = 6.7, 2 H), 4.30-4.12 (m, 6 H), 3.70-3.58 (m, 4 H), 3.11 (dd, J= 10.4, 6.9, 2 H), 2.98-2.92 (m, 2 H), 2.17-1.88 (m, 8 H), 1.85-1.77 (m, 2 H), 1.64-1.54 (m, 2 H), 1.38-1.15 (m, 12 H), 0.86 (t, J= 6.9, 6 H), NH not assigned.

[0393] 'H-NMR (600 MHz, DMSO-d6, minor isomers): 5.42-5.28 (m, 4 H), 4.45-4.37 (m, 2 H), 4.30-4.12 (m, 4 H), 3.85-3.78 (m, 2 H), 3.70-3.58 (m, 4 H), 3.19 (dd, J= 10.0, 6.9, 2 H), 2.83-2.76 (m, 2 H), 2.17-1.88 (m, 10 H), 1.77-1.68 (m, 2 H), 1.38-1.15 (m, 12 H), 0.86 (t, J= 6.9, 6 H), NH not assigned.

[0394] 13C-NMR (150.9 MHz, DMSO-d6, major isomers): 171.35, 130.23, 128.45, 69.95, 68.04, 63.99 and 63.98, 63.63 and 63.60, 36.59, 36.45 and 36.44, 30.81, 28.69, 26.50, 25.12, 21.89, 13.84.

[0395] 13C-NMR (150.9 MHz, DMSO-d6, minor isomers): 170.79, 130.35, 128.38, 70.54, 67.98, 64.92 and 64.91, 63.82 and 63.78, 36.74, 34.89, 30.81, 28.67, 26.50, 25.28, 21.89, 13.84.

[0396] Example 2

[0397] Biodegradability measurement of the invention’s compounds and of comparative compounds

[0398] The biodegradability of precursor compounds of formula (I) was compared to that of a series of comparative compounds using the OECD 301F (‘manometric respirometry’) biodegradation test according to the Organisation for Economic Co-operation and Development (OECD) guideline for the testing of materials (No. 301 F, Paris 1992). Test results are listed in Table 1.

[0399] Table 1: Biodegradation of compounds of formula (I) and of comparative compounds determined according to the OECD 30 IF biodegradation test.

[0400] When based on the same compound of formula (II) to be released, ethyl thiazolidine-4- carboxylates (Compounds 2 and 4) and thiazolidine-4-carboxylic acids (Compound 5) derived from L-cysteine according to formula (I) are more readily biodegradable than the corresponding ethyl oxazolidine-4-carboxylates (Compounds A and B) derived from L-serine. Unsubstituted ethyl thiazolidine-4-carboxylates (Compound 4) according to formula (I) are also more readily biodegradable than the corresponding ethyl thiazolidine-4-carboxylates substituted either at the N atom (Compound C) or at the 5 -position of the heterocycle (Compound D).

[0401] Example 3

[0402] Performance of a fabric softener base comprising an invention’s compound of formula (I)

[0403] The performance of the present invention’s compounds of formula (I) was tested in a fabric softening surfactant emulsion with the following final composition:

[0404] Stepantex® VL90 A (origin: Stepan) 12.21 % by weight Calcium chloride (10% aq. solution) 0.40 % by weight Proxel® GXL (origin: Avecia) 0.04 % by weight Water 87.35 % by weight

[0405] Dynamic headspace measurements

[0406] The invention’s precursor compound of formula (I) (0.1 mmol) was dissolved in ethanol, ethyl acetate, DMSO or water (0.2 mL) and completed to 7.0 g of the above-described fabric softener formulation. After homogenization, an aliquot of the sample (0.07 g) was placed in a flask and diluted with demineralized cold tap water (23.0 g). Then, one cotton sheet (EMPA coton test cloth Nr. 221, origin: Eidgenossische Materialpriifanstalt), pre-washed with an unperfumed detergent powder and cut to ca. 15 x 15 cm sheets, ca. 5.2 g) was added and shaken manually for 3 min, left standing for 2 min, then wrung out by hand, and weighed (ca. 10.0 g) to obtain a constant quantity of residual water. A reference sample consisting of an equimolar amount of the corresponding unmodified compound of formula (II) to be released form the precursor compound of formula (I) was prepared and analyzed the same way. The cotton sheets were line-dried for 1 or 3 days before being analyzed. For the measurements, the sheets were put into a headspace sampling cell (ca. 160 mL inner volume), which were thermostated at 25°C and exposed to a constant air flow of ca. 200 mL / min. The air was filtered through active charcoal and aspirated through a saturated solution of NaCl (to ensure a constant humidity of the air of ca. 75%). The system was equilibrated during 15 min while adsorbing the volatiles on a waste Tenax® cartridge. Then, seven times consecutively, the volatiles were adsorbed for 15 min on a clean Tenax® cartridge and for 45 min on a waste Tenax® cartridge. A final data point was collected by adsorbing the volatiles for 15 min on a clean Tenax® cartridge. Altogether eight data points were collected. Each cartridge contained 100 mg of poly(2,6-diphenyl- -phenylene oxide) (Tenax® TA). The waste cartridges were discarded; the other cartridges were desorbed on a Perkin Elmer TurboMatrix ATD thermo desorb er coupled to an Agilent Technologies 7890A gas chromatograph equipped with a HP-1 capillary column (30 m, i.d. 0.32 mm, film 0.25 pm) and a flame ionization detector. The volatiles were analyzed using a temperature gradient moving from 80°C to 260°C at 15°C / min. Headspace concentrations (in ng / L air) were obtained by external standard calibrations using different concentrations of the fragrance to be released in ethanol. Each calibration solution (0.2 pL) was injected onto a clean Tenax® cartridge, which was desorbed and analyzed under the same conditions. Table 2 lists the sum of the headspace concentrations collected from the eight data points for the release of the respective compounds of formula (II) as compared to an equimolar amount of the corresponding unmodified compounds of formula (II) above dry coton after line-drying for 1 day; the corresponding data recorded after 3 days are listed in Table 3. All values are average values of at least two measurements.

[0407] Table 2: Average headspace concentrations (sum of eight data points) of compounds of formula (II) measured on dry coton after line-drying for 1 day after a fabric softener application. Table 3: Average headspace concentrations (sum of eight data points) of compounds of formula (II) measured on dry cotton after line-drying for 3 days after a fabric softener application. Precursors according to formula (I) released higher quantities of aldehydes or ketones according to formula (II) into the headspace than the corresponding unmodified reference compound of formula (II). Compounds of formula (I) according to the present invention are capable to increase the long-lastingness of active aldehydes or ketones.

[0408] When based on the same compound of formula (II), thiazolidine-4-carboxylates derived from L-cysteine according to formula (I) released higher amounts of compounds of formula (II) into the headspace above dry cotton than the corresponding oxazolidine-4-carboxylates. Furthermore, precursor compounds of formula (I) with an unsubstituted NH group in the heterocycle (e.g. Compound 4) were found to be considerably more efficient than the corresponding N-substituted comparative compound (e.g. Compound C).

[0409] Example 4

[0410] Preparation of a perfume oil

[0411] A non-limiting example of a typical perfume oil is prepared by admixing the following perfuming co-ingredients:

[0412] Ingredients weight-%

[0413] Ethyl 2-methylbutanoate 0.16

[0414] Hexyl acetate 0.37

[0415] Limonene 1.67

[0416] 2.6-Dimethyl-7-octen-2-ol 0.94

[0417] 2 -Phenyl ethanol 2.15

[0418] Linalool 0.73

[0419] (2RS,4SR / 4RS)-4-Methyl-2-(2-methyl-l-propen-l-yl)tetrahydro-2H-pyran 0.30

[0420] Ethyl 2-methyl-l,3-dioxolane-2-acetate 0.32

[0421] Benzyl acetate 2.46

[0422] Allyl heptanoate 0.38 alpha-Terpineol 0.88

[0423] 3.7-Dimethyl-6-octen-l-ol 0.55 4-Methoxybenzaldehyde 1.00

[0424] ( / / )-4-Methyl-3-decen-5-ol 0.37

[0425] [cis / trans-4-(2-Propanyl)cyclohexyl]methanol 0.47

[0426] 1-Methoxy-4-[(lE)-l-propen-l-yl]benzene 0.15

[0427] (lRS,2RS / 2SR)-2-(2-Methyl-2-propanyl)cyclohexyl acetate 1.95 l,l-Dimethyl-2-phenyl ethyl acetate 0.95

[0428] Tricyclo[5.2.1.02’~]dec-3 / 4-en-8-yl acetate 3.34

[0429] Allyl 3-cyclohexylpropanoate 0.26

[0430] 3 -(4-Isopropylphenyl)-2-methylpropanal 8.18

[0431] (3E)-3-Methyl-4-(2,6,6-trimethyl-2-cyclohexen-l-yl)-3-buten-2-one and (1E)-

[0432] 1 -(2,6,6-trimethyl-2-cyclohexen- 1 -yl)- 1 -penten-3 -one 1.13

[0433] 2 -Phenoxy ethyl 2-methylpropanoate 5.38

[0434] Tricyclo[5.2.1.0(2,6)]dec-3 / 4-en-8-yl propanoate 2.32

[0435] 5-Heptyldihydro-2(3H)-furanone 2.30

[0436] 2 / 3 -Methylbutyl salicylate 1.42

[0437] (3Z)-3-Hexen-l-yl salicylate 0.31 l-(2,3,8,8-Tetramethyl-l,3,4,5,6,7-hexahydronaphthalen-2-yl)ethanone 16.03

[0438] Hexyl 2-hydroxybenzoate 5.04

[0439] (2E)-2-Benzylideneoctanal 21.22

[0440] (-)-(3aR,5aS,9aS,9bR)-3a,6,6,9a-Tetramethyldodecahydronaphtho[2,l-b]furan 0.27

[0441] 1 -Oxa- 12 / 13 -cyclohexadecen-2-one 4.78

[0442] Oxacyclohexadecan-2-one 3.82

[0443] Benzyl 2-hydroxybenzoate 3.01

[0444] Dipropylene glycol 5.39

[0445] Total: 100

[0446] Example 5

[0447] Preparation of transparent isotropic shampoo formulations comprising an invention’s compound of formula (I)

[0448] A typical unperfumed transparent isotropic shampoo formulation is listed in Table 4. The unperfumed shampoo formulation is prepared by dispersing Polyquatemium-10 in water. The remaining ingredients of Phase A are mixed separately by addition of one after the other while mixing well after each adjunction. This pre-mix is added to the Polyquatemium-10 dispersion and mixed for another 5 min. Then, the premixed Phase B and the premixed Phase C are added (Monomuls® 90L-12 is heated to melt in Texapon® NSO IS) while agitating. Phase D and Phase E are added while agitating. The pH is adjusted with a citric acid solution to 5.5-6.0.

[0449] Table 4: Composition of a typical unperfumed transparent isotropic shampoo formulation.

[0450] (1)Ucare® Polymer JR-400; origin: Noveon (2)Origin: Brenntag Schweizerhall AG

[0451] (3)Glydant®; origin: Lonza

[0452] (4)Texapon® NSO IS; origin: Cognis

[0453] (5)Tego® Betain F 50; origin: Evonik

[0454] (6)Amphotensid GB 2009; origin: Zschimmer & Schwarz (7)Brij® S20; origin: Croda

[0455] (8)Monomuls® 90 L-12; origin: Gruenau GmbH

[0456] (9)Nipagin Monosodium; origin: NIPA The perfumed shampoo formulation is then obtained by adding, under gentle shaking, a perfume oil of Example 4 (0.1 to 0.8% by weight relative to the total weight of the unperfumed shampoo formulation) and at least one of the compounds of formula (I) (0.05 to 0.50% by weight relative to the total weight of the unperfumed shampoo formulation) into the unperfumed shampoo formulation listed in Table 4.

[0457] Example 6

[0458] Preparation of pearly shampoo formulations comprising an invention’s compound of formula (I)

[0459] A typical unperfumed pearly shampoo formulation is listed in Table 5. The unperfumed shampoo formulation is prepared by dispersing Tetrasodium EDTA, Guar hydroxypropyltrimonium chloride and Polyquatemium-10 in water. NaOH (10% aqueous solution, Phase B) is added once Phase A is homogeneous. Then, the premixed Phase C is added, and the mixture heated to 75°C. Phase D ingredients are added and mixed until the mixture is homogeneous. The mixture is cooled. At 45 °C, Phase E ingredients are added while mixing. The final viscosity is adjusted with NaCl (25% aqueous solution) and a pH of 5.5-6.0 is adjusted with NaOH (10% aqueous solution).

[0460] Table 5: Composition of a typical pearly shampoo formulation.

[0461] (1)EDETA® B Powder; origin: BASF

[0462] (2)Jaguar® C14 S; origin: Rhodia

[0463] (3)Ucare® Polymer JR-400; origin: Noveon

[0464] (4)Sulfetal® LA B-E; origin: Zschimmer & Schwarz

[0465] (5)Zetesol® LA; origin: Zschimmer & Schwarz

[0466] (6)Tego® Betain F 50; origin: Evonik

[0467] (7)Xiameter® MEM-1691; origin: Dow Coming

[0468] (8)Lanette® 16; origin: BASF

[0469] (9)Comperlan® 100; origin: Cognis

[0470] (10)Cutina® AGS; origin: Cognis

[0471] (11)Kathon® CG; origin: Rohm & Haas

[0472] <12) D-Panthenol; origin: Roche

[0473] A perfumed pearly shampoo formulation is then obtained by adding, under gentle shaking, a perfume oil (as e.g. described in Example 4, 0.1 to 0.8% by weight relative to the total weight of the unperfumed shampoo formulation) and at least one of the compounds of formula (I) (0.05 to 0.50% by weight relative to the total weight of the unperfumed shampoo formulation) into the unperfumed pearly shampoo formulation listed in Table 5.

[0474] Example 7

[0475] Preparation of rinse-off hair conditioner formulations comprising an invention’s compound of formula (I)

[0476] A typical unperfumed rinse-off hair conditioner formulation is listed in Table 6. The unperfumed rinse-off hair conditioner formulation is prepared by mixing the ingredients of Phase A until an uniform mixture was obtained. Tylose® is allowed to completely dissolve. Then the mixture is heated to 70-75°C. The ingredients of Phase B are combined and melted at 70-75°C. Then the ingredients of Phase B are added to Phase A with good agitation, and the mixing is continued until that the mixture has a temperature of 60°C. Then, the ingredients of Phase C are added while agitating and keeping mixing until the mixture cooled to 40°C. The pH is adjusted with a citric acid solution to 3.5-4.0.

[0477] Table 6: Composition of a typical rinse-off hair conditioner formulation.

[0478] (1)Genamin® KDMP; origin: Clariant

[0479] (2)Tylose® H10 Y G4; origin: Shin Etsu

[0480] (3)Lanette® O; origin: BASF

[0481] (4)Arlacel® 165 ; origin: Croda

[0482] (5)Incroquat® Behenyl TMS-50-PA- (MH); origin: Croda

[0483] (6) Brij® S20; origin: Croda

[0484] (7)Xiameter® MEM-949; origin: Dow Coming

[0485] <8) Origin: Alfa Aesar

[0486] A perfumed rinse-off hair conditioner formulation is then obtained by adding, under gentle shaking, a perfume oil (as e.g. described in Example 4, 0.2 to 1.0% by weight relative to the total weight of the unperfumed conditioner formulation) and at least one of the compounds of formula (I) (0.05 to 0.5% by weight relative to the total weight of the unperfumed conditioner formulation) into the unperfumed rinse-off hair conditioner formulation listed in Table 6.

[0487] Example 8

[0488] Preparation of structured shower gel formulations comprising an invention’s compound of formula (I)

[0489] A typical unperfumed structured shower gel formulation is listed in Table 7. A perfumed structured shower gel is prepared by adding, under gentle shaking, a perfume oil (as e.g. described in Example 4, 0.1 to 1.5% by weight relative to the total weight of the structured shower gel) and at least one of the invention’s compounds of formula (I) (0.05 to 0.50% by weight relative to the total weight of the structured shower gel) into the unperfumed structured shower gel formulation of Table 7.

[0490] Table 7: Composition of a typical unperfumed structured shower gel formulation.

[0491] (1)EDETA B powder; origin: BASF

[0492] (2)Carbopol Aqua SF-1 polymer; origin: Noveon

[0493] (3)Zetesol AO 328 U; origin: Zschimmer & Schwarz

[0494] (4)Tego Betain F 50; origin: Goldschmidt

[0495] (5)Kathon® CG; origin: Rohm & Haas

[0496] Example 9 Preparation of transparent shower gel formulations comprising an invention’s compound of formula (I)

[0497] A typical unperfumed transparent shower gel formulation is listed in Table 8. A perfumed transparent shower gel is prepared by adding, under gentle shaking, a perfume oil (as e.g. described in Example 4, 0.5 to 1.5% by weight relative to the total weight of the transparent shower gel) and at least one of the invention’s compounds of formula (I) (0.05 to 0.50% by weight relative to the total weight of the transparent shower gel) into the unperfumed transparent shower gel formulation of Table 8.

[0498] Table 8: Composition of a typical unperfumed transparent shower gel formulation

[0499] (1)EDETA B powder; origin: BASF

[0500] (2)Zetesol AO 328 U; origin: Zschimmer & Schwarz

[0501] (3)Tego Betain F 50; origin: Goldschmidt

[0502] (4)Merquat® 550; origin: Lubrizol

[0503] Example 10

[0504] Preparation of milky shower gel formulations comprising an invention’s compound of formula (I)

[0505] A typical unperfumed milky shower gel formulation is listed in Table 9. A perfumed milky shower gel is prepared by adding, under gentle shaking, a perfume oil (as e.g. described in Example 4, 0.1 to 1.5% by weight relative to the total weight of the milky shower gel) and at least one of the invention’s compounds of formula (I) (0.05 to 0.50% by weight relative to the total weight of the milky shower gel) into the unperfumed milky shower gel formulation of Table 9.

[0506] Table 9: Composition of a typical unperfumed milky shower gel formulation.

[0507] (1)EDETA® B powder; origin: BASF

[0508] (2)Texapon® NSO IS; origin: Cognis

[0509] (3)Merquat® 550; origin: Lubrizol (4)Dehyton® AB-30; origin: Cognis

[0510] (5)Glucamate® LT; origin: Lubrizol

[0511] (6)Euperlan® PK 3000 AM; origin: Cognis

[0512] (7)Cremophor® RH 40; origin: BASF

[0513] Example 11

[0514] Preparation of anhydrous antiperspirant spray formulations comprising an invention’s compound of formula (I) A typical unperfumed anhydrous antiperspirant spray formulation is listed in Table 10. The anhydrous antiperspirant spray formulation is prepared by using a high-speed stirrer. Silica and Quatemium-18-hectorite are added to the mixture of isopropyl myristate and cyclomethicone. Once completely swollen, aluminium chlorohydrate is added portion-wise under stirring until the mixture becomes homogeneous and without lumps.

[0515] Table 10: Composition of a typical unperfumed anhydrous antiperspirant spray.

[0516] (1)Dow Coming® 345 Fluid; origin: Dow Coming

[0517] (2)Aerosil® 200 ; origin: Evonik

[0518] (3)Bentone® 38; origin: Elementis Specialities

[0519] (4)Micro Dry Ultrafine; origin: Reheis

[0520] The perfumed formulation is then obtained by adding a perfume oil (as e.g. described in Example 4, 0.85% by weight relative to the total weight of the antiperspirant spray formulation) and at least one of the invention’s compounds of formula (I) (0.15% by weight relative to the total weight of the antiperspirant spray formulation) into the unperfumed antiperspirant spray formulation of Table 10.

[0521] Example 12

[0522] Preparation of deodorant spray emulsion formulations comprising an invention’s compound of formula (I)

[0523] A typical deodorant spray emulsion formulation is prepared by mixing and dissolving all the ingredients according to the sequence of Table 11. Then a perfume oil (as e.g. described in Example 4, 1.35% by weight relative to the total weight of the deodorant spray formulation) and at least one of the invention’s compounds of formula (I) (0.10 to 0.20% by weight relative to the total weight of the deodorant spray formulation) are added under gentle shaking. Then aerosol cans are filled, and the propellant is crimped and added. Aerosol filling: 40% active solution 60% propane / butane (2.5 bar).

[0524] Table 11 : Composition of a typical unperfumed deodorant spray formulation.

[0525] (1)Irgasan® DP 300; origin: BASF

[0526] Example 13

[0527] Preparation of deodorant stick formulations comprising an invention’s compound of formula (I)

[0528] A typical unperfumed deodorant stick formulation is listed in Table 12. The deodorant stick formulation is obtained by weighing all the components of Part A and heating to 70-75°C. Ceteareth-25 is added once the other Part A ingredients are mixed and heated. Once the Ceteareth-25 is dissolved, stearic acid is added. Part B is prepared by dissolving Triclosan in 1,2-propylene glycol. Evaporated water is compensated. Then, slowly, under mixing, Part B is poured into Part A.

[0529] Table 12: Composition of a typical unperfumed deodorant stick formulation.

[0530] (1)Edeta® B Power; origin: BASF

[0531] (2)Cremophor® A25; origin: BASF

[0532] (3)Tegosoft® APM; origin: Evonik

[0533] (4)Irgasan® DP 300; origin: BASF

[0534] The perfumed deodorant stick formulation is then obtained by adding perfume oil (as e.g. described in Example 4, 0.85% by weight relative to the total weight of the deodorant stick formulation) and at least one of the invention’s compounds of formula (I) (0.10 to 0.20% by weight relative to the total weight of the deodorant stick formulation) under gentle shaking. To stock, a plastic bag is put into the bucket to be sealed after cooling. Moulds were filled at about 70°C.

[0535] Example 14

[0536] Preparation of deodorant roll-on formulations comprising an invention’s compound of formula (I)

[0537] A typical unperfumed deodorant roll-on formulation is listed in Table 13. Part A is prepared by sprinkling little-by-little the hydroxyethylcellulose into the water, whilst rapidly stirring with a turbine until the hydroxyethylcellulose is entirely swollen giving a limpid gel. Part B is slowly poured into Part A, whilst continuing stirring until the entire mixture is homogeneous. Then Part C is added.

[0538] Table 13: Composition of a typical unperfumed deodorant roll-on formulation.

[0539] (1)Natrosol® 250 H; origin: Ashland

[0540] (2)Irgasan® DP 300; origin: BASF

[0541] (3)Cremophor® RH 40; origin: BASF

[0542] The perfumed deodorant roll-on formulation is then obtained by adding perfume oil of Example 4 (0.85% by weight relative to the total weight of the deodorant stick formulation) and at least one of the invention’s compounds of formula (I) (0.10-0.20% by weight relative to the total weight of the deodorant stick formulation) under gentle shaking.

[0543] Example 15

[0544] Preparation of day cream base O / W emulsions comprising an invention’s compound of formula (I)

[0545] A typical day cream base O / W emulsion formulation comprising an invention’s compound of formula (I) is listed in Table 14. Phases A and B are heated separately to 70-75 °C, then Phase A is added to Phase B and vacuum is applied. The mixture is stirred and cooled to 55 °C for 15 min. After cooling to room temperature, phenoxyethanol (and) piroctone olamine (Part C) are added when a temperature of 45 °C is reached. The mixture is stirred for 5 min before sodium carbomer (Part D), a perfume oil (as e.g. described in Example 4) and at least one of the invention’s compounds of formula (I) (Part E) are added. The mixture is stirred for 3 min, then the stirring was stopped for 15 min. When the temperature of the mixture reaches 30°C, the stirring is resumed for another 15 min until the cream becomes homogeneous, glossy and without lumps. If necessary the pH is adjusted to 6.70-7.20 with Glydant®, Phenoni®p or Nipaguard® PO5 or to 6.30-7.00 with Nikkoguard®.

[0546] Table 14: Composition of a typical day cream base O / W emulsion.

[0547] (1)Arlacel® 985; origin: Croda

[0548] (2)Tefose® 2561; origin: Gattefosse

[0549] (3)Biolip P 90; origin: Gattefosse

[0550] (4)Mineral oil 30-40 CPS (5)Petroleum jelly

[0551] (6)Nipaguard® PO 5; origin: Clariant

[0552] (7)PNC 400

[0553] Example 16

[0554] Preparation of hand dishwash formulations comprising an invention’s compound of formula (I)

[0555] A typical unperfumed hand dishwash formulation is listed in Table 15. The unperfumed hand dishwash is prepared by mixing water with sodium hydroxide and di ethanolamide. Then the linear alkylbenzene sulfonic acid is added. After neutralizing, the remaining ingredients are added and the pH is adjusted to 7-8 if necessary.

[0556] Table 15: Composition of a typical unperfumed hand dishwash formulation.

[0557] (1)Biosoft® S-118; origin: Stepan

[0558] (2)Ninol® 40-CO; origin: Stepan

[0559] (3)Stepanate® SXS; origin: Stepan

[0560] (4)Tergitol® 15-S-9; origin: Dow Chemicals

[0561] The perfumed hand dishwash formulation is then obtained by adding perfume oil (as e.g. described in Example 4, 0.85% by weight relative to the total weight of the hand dishwash formulation) and at least one of the invention’s compounds of formula (I) (0.10 to 0.20% by weight relative to the total weight of the dishwash formulation) under gentle shaking into the unperfumed hand dishwash formulation of Table 15.

[0562] Example 17

[0563] Preparation of liquid detergent formulations comprising an invention’s compound of formula m

[0564] A typical liquid detergent formulation is prepared by mixing the ingredients listed in Table 16. Then a perfume oil (as e.g. described in Example 4, 0.3 to 0.8% by weight relative to the total weight of the liquid detergent) and at least one of the invention’s compounds of formula (I) (0.05 to 1.0% by weight relative to the total weight of the liquid detergent) are added under gentle shaking into the unperfumed liquid detergent formulation of Table 16.

[0565] Table 16: Composition of a typical unperfumed liquid detergent formulation.

[0566]

[0567] (1)Hostapur® SAS 60; origin: Clariant

[0568] (2)Edenor® K 12-18; origin: Cognis

[0569] (3)Genapol® LA 070; origin: Clariant

[0570] (4)Origin: Genencor International

[0571] (5)Aculyn® 88; origin: Dow Chemicals

[0572] Example 18

[0573] Performance of a liquid detergent base comprising an invention’s compound of formula (I)

[0574] Dynamic headspace measurements

[0575] The invention’s precursor compound of formula (I) (dosed to release a total of 0.07 mmol of the compound of formula (II)) was dissolved in ethanol (0.1 mL) and completed to 4.5 g with an unperfumed standard liquid detergent formulation (Le Chat Sensitive 0%, origin: Henkel). The sample was strongly shaken (lOx) to homogenize. After homogenization, an aliquot of the sample (0.45 g) was placed in a stainless steel container of a Linitest® washing machine (Original Hanau Linitest®, origin: Heraeus AG) and diluted with demineralized cold tap water (120 g). After shaking (lOx), four cotton sheets (EMPA cotton test cloth Nr. 221, origin: Eidgendssische Materialprufanstalt), pre-washed with an unperfumed detergent powder and cut to ca. 15 x 15 cm sheets, ca. 5.2 g) were added. The container was closed, shaken manually (5x), placed inside the Linitest® machine and agitated mechanically in a water bath (ca. 40°C) for 1 h. Then the container was removed and the washing water decanted. The four cotton sheets were twice rinsed with demineralized cold tap water (200 g) and left for 5 min with occasional shaking. Then each cotton sheet was wrung out by hand and weighed (ca. 10.0 g) to obtain a constant quantity of residual water. A reference sample consisting of an equimolar amount of the corresponding unmodified compound of formula (II) to be released form the precursor compound of formula (I) was prepared and analyzed the same way. The cotton sheets were line-dried for 1 or 3 days before being analyzed. Headspace sampling of the volatiles evaporating from the cotton surface onto Tenax® cartridges was performed as described in Example 3. The cartridges were desorbed on a Markes TD100-XR thermo desorb er coupled to an Agilent Technologies 7890A gas chromatograph equipped with a Supelco MDN-1 capillary column (30 m, i.d. 0.32 mm, film 1 pm) and a flame ionization detector. The volatiles were analyzed using a temperature gradient moving from 60°C (for 1 min) to 250°C at 10°C / min. Headspace concentrations (in ng / L air) were obtained by external standard calibrations using different concentrations of the fragrance to be released in ethanol. Each calibration solution (0.2 pL) was injected onto a clean Tenax® cartridge, which was desorbed and analyzed under the same conditions. Table 17 lists the sum of the headspace concentrations collected from the eight data points for the release of the respective compounds of formula (II) as compared to the corresponding unmodified compounds of formula (II) above dry cotton after line-drying for 1 day; the corresponding data recorded after 3 days are listed in Table 18. All values are average values of at least two measurements.

[0576] Table 17: Average headspace concentrations (sum of eight data points) of compounds of formula (II) measured on dry cotton after line-drying for 1 day after a liquid detergent application.

[0577] Table 18: Average headspace concentrations (sum of eight data points) of compounds of formula (II) measured on dry cotton after line-drying for 3 days after a liquid detergent application.

[0578] Precursors according to formula (I) released higher quantities of aldehydes or ketones according to formula (II) into the headspace than the corresponding unmodified reference compound of formula (II). Compounds of formula (I) according to the present invention are capable to increase the long-lastingness of active aldehydes or ketones.

[0579] When based on the same compound of formula (II), thiazolidine-4-carboxylates derived from L-cysteine according to formula (I) released higher amounts of compounds of formula (II) into the headspace above dry cotton than the corresponding comparative compound bearing substituents at the 5-position of the heterocycle (e.g. Compound D). Example 19

[0580] Performance of the invention’s compounds of formula (I) in a liquid detergent application

[0581] The invention's compounds of formula (I) were added to an unperfumed standard liquid detergent formulation (Le Chat Sensitive 0%, origin: Henkel) and their performance evaluated olfactively on fabric after a machine washing cycle. For the tests, a washing machine (Miele WMB 100-20 CH) was loaded with about 2.5 kg of fabric composed of 18 cotton towels, 18 cotton T-shirts and 12 polyester T-shirts. The liquid detergent (50 g) containing the compounds of formula (I) or, alternatively, an equivalent of the corresponding fragrance as a reference was loaded into the corresponding drawer of the washing machine. The fabric was washed at 40°C without a pre-washing cycle, followed by two rinse cycles and spun at 900 rotations per minute (ca. 1 h 24 min). The fabric was then line dried for 1 day at 20.5°C and an ambient humidity of 50%, before being stored in aluminum foil and being olfactively evaluated after 7 days by an expert panel. The panelists (9-10 persons) rated the olfactive intensity of the released fragrance at a scale from 0 (imperceptible) to 10 (very intense) against that of the reference sample. The dosages of the compounds of formula (I) and of the reference fragrance in the liquid detergent, as well as the average intensities perceived by the panelists on the different substrates are indicated in Table 19.

[0582] Table 19: Perceived average olfactive intensities of compounds of formula (I) in a liquid detergent application as compared to the corresponding reference fragrance.

[0583]

[0584] The data in Table 19 show that the invention's compound of formula (I) generally performed better than the corresponding reference sample in a liquid detergent application by providing a long-lasting fragrance effect to various types of substrates.

[0585] Example 20

[0586] Performance of the invention’s compounds of formula (I) in a fabric softening application

[0587] The invention's compounds of formula (I) were added to an unperfumed standard fabric softening formulation with the following final composition:

[0588] Stepantex® VL90 A (origin: Stepan) 8.88 % by weight Calcium chloride (10% aq. solution) 0.36 % by weight Proxel® GXL (origin: Avecia) 0.04 % by weight Water 90.72 % by weight

[0589] The performance of the compounds of formula (I) was then evaluated olfactively on fabric after a machine washing and softening cycle. For the tests, a washing machine (Miele WMB 100-20 CH) was loaded with about 2.5 kg of fabric composed of 18 cotton towels, 18 cotton T-shirts and 12 polyester T-shirts. An unperfumed liquid detergent (Le Chat Sensitive 0%, origin: Henkel, 50 g) was loaded into the detergent drawer of the washing machine and an unperfumed fabric softener formulation (30 g) containing the compounds of formula (I) or, alternatively, an equivalent of the corresponding fragrance as a reference, into the fabric enhancer compartment. The fabric was washed at 40°C with a short washing cycle and one rinse cycle and spun at 900 rotations per minute (ca. 20 min) and followed by the fabric softening cycle. The fabric was then line dried for 1 day at 20.5°C and an ambient humidity of 50%, before being stored in aluminum foil and being olfactively evaluated after 7 days by an expert panel. The panelists (9-10 persons) rated the olfactive intensity of the released fragrance at a scale from 0 (imperceptible) to 10 (very intense) against that of the reference sample. The dosages of the compounds of formula (I) and of the reference fragrance in the fabric softener, as well as the average intensities perceived by the panelists on the different substrates are indicated in Table 20.

[0590] Table 20: Perceived average olfactive intensities of compounds of formula (I) in a fabric softener application as compared to the corresponding reference fragrance. The data in Table 20 show that the invention's compound of formula (I) generally performed better than the corresponding reference sample in a fabric softener application by providing a long-lasting fragrance effect to various types of substrates.

Claims

Claims1. A method to release from a precursor compound of formula (I), an aldehyde or a ketone of formulawherein the compound of formula (II) comprises at least 8 carbon atoms;R1is a phenyl, a benzyl, a benzo[d][l,3]dioxole or a naphthyl group; with the phenyl and benzyl group being optionally substituted with one or more of a C1-8 alkyl, C1-8 alkoxy, hydroxy and / or C1-4 carboxylic ester group, or R1is a group of formulawherein the dashed line represents a single or a double bond; R3is a C2-12 hydrocarbon group optionally comprising one or two oxygen atoms; R4and R5, independently from each other, are a hydrogen atom or a C1-6 alkyl group; or R3and R4or R3and R5, when taken together, form a C5-15 cycloalkyl, C5-15 cycloalkenyl, C4-14 heterocycloalkyl or C4-14 heterocycloalkenyl group, each optionally substituted with one or more of a C1-15 hydrocarbon group, optionally comprising one or more oxygen atoms, wherein the heteroatom represents one or more oxygen atoms;R2represents a hydrogen atom or a C1-15 hydrocarbon group;R1and R2, when taken together, form a C5-15 cycloalkyl or C5-15 cycloalkenyl group wherein the double bond is not conjugated with the ketone functional group, a C4-14 heterocycloalkyl or C4-14 heterocycloalkenyl group wherein the double bond is not conjugated with the ketone functional group, each optionally substituted with one or more of a C1-15 alkyl, C1-15 alkoxy, C3-15 cycloalkyl, C5-15 cycloalkenyl, Ce-io aryl and / or Ce-io aryloxy group, each optionally substituted with one or more of a Ci-s alkyl, C1-8 alkoxy and / or C1-4 carboxylic ester group, wherein the heteroatom represents one or more oxygen atoms; wherein the precursor compound comprises a compound of formulain the form of any one of its stereoisomers or a mixture thereof, and wherein R1and R2have the same meaning as defined above; n is 1, 2, 3 or 4; X is an oxygen atom or a NR7group wherein R7is a hydrogen atom or a Ci-6 alkyl group; R6is a hydrogen atom, a sodium, potassium or ammonium cation or a Ci-i6 hydrocarbon group optionally containing one to nine oxygen atoms; by exposing the precursor compound of formula (I) to trace of water.

2. The method according to claim 1, wherein the compound of formula (I) is a C11-C70 compound, preferably a C15-36 compound.

3. The method according to any one of claims 1 to 2, wherein X is an oxygen atom and n is 1.

4. The method according to any one of claims 1 to 3, wherein R6is a hydrogen atom, a sodium cation or a C1-4 alkyl group; preferably R6is a hydrogen atom or a methyl or ethyl group.

5. The method according to any one of claims 1 to 4, wherein R2is a hydrogen atom or a C1-12 hydrocarbon group; preferably, R2is a hydrogen atom or a C1-10 hydrocarbon group; preferably, R2is a hydrogen atom or a Ci-s hydrocarbon group; preferably, R2is a hydrogen atom or a C1-6 hydrocarbon group; preferably, R2is a hydrogen atom or a C1-6 alkyl or C2-6 alkenyl group; preferably, R2is a hydrogen atom or a C1-4 alkyl or C2-4 alkenyl group; preferably, R2is a hydrogen atom or a C1-3 alkyl group; preferably, R2is a hydrogen atom or a methyl or ethyl group; preferably R2is a hydrogen atom.

6. The method according to any one of claims 1 to 5, wherein R1comprises between 8 and 18 carbon atoms and is a group of formula (a) wherein R3is a C4-12 hydrocarbon group optionally comprising one or two oxygen atoms; R4and R5, independentlyfrom each other, are a hydrogen atom or a C1-4 alkyl group; preferably at least one of R4and R5is a Ci-4 alkyl group; or R3and R5or R3and R4, when taken together, form a C5-6 cycloalkyl or C5-6 cycloalkenyl group, each optionally substituted with one or more of a Ci-s alkyl or Ci-s alkenyl group.

7. Use of a compound of formula (I) as defined in claims 1 to 6 as a perfuming ingredient to provide a long-lasting odor.

8. A method to confer, enhance, improve or modify the odor properties of a perfuming composition, the air surrounding the perfuming composition, a surface or a perfumed article, comprising adding to the composition, the air, or article, or contacting or treating the surface with an effective amount of at least one compound of formula (I) as defined in claims 1 to 6.

9. A method for intensifying or prolonging the diffusion effect of the characteristic fragrance of at least one aldehyde or ketone compound of formula (II), as defined in claims 1 to 6, on a surface or the air surrounding a perfuming composition, wherein the surface, or the air is treated with at least one compound of formula (I) as defined in claims 1 to 6, or with a composition or article containing at least one compound of formula (I), under conditions susceptible of allowing the release of at least one ketone or aldehyde compound formula (II), over time.

10. A perfuming composition comprising i) at least one compound of formula (I), as defined in any one of claims 1 to 6; ii) at least one ingredient selected from the group consisting of a perfumery carrier and a perfumery base; and iii) optionally at least one perfumery adjuvant.

11. A perfumed consumer product comprising at least one compound of formula (I), as defined in any one of claims 1 to 6 or a perfuming composition as defined in claim 10.

12. The perfumed consumer product according to claim 11, wherein the perfumery consumer product is a perfume, a fabric care product, a body-care product, a cosmeticpreparation, a skin-care product, an air care product or a home care product.

13. The perfumed consumer product according to claim 12, wherein the perfumery consumer product is a fine perfume, a splash or eau de parfum, a cologne, a shave or aftershave lotion, a liquid or solid detergent optionally in the form of a pod or tablet, a fabric softener, a liquid or solid scent booster, a dryer sheet, a fabric refresher, an ironing water, a paper, a bleach, a carpet cleaner, a curtain-care product, a shampoo, a leave-on or rinse-off hair conditioner, a coloring preparation, a color-care product, a hair shaping product, a dental care product, a disinfectant, an intimate care product, a hair spray, skin cream or lotion, a vanishing cream, a deodorant or antiperspirant, a hair remover, a tanning or sun or after sun product, a nail product, a skin cleansing, a makeup, a perfumed soap, a shower or bath mousse, oil or gel, a foot / hand care product, a hygiene product, an air freshener, a “ready to use” powdered air freshener, a mold remover, a furnisher care, a wipe, a dish detergent or hard-surface detergent, a leather care product, a car care product.

14. A compound of formulain the form of any one of its stereoisomers or a mixture thereof, and whereinR1comprises between 8 and 18 carbon atoms and is a group of formulawherein the dashed line represents a single or a double bond; R3is a C4-12 hydrocarbon group optionally comprising one or two oxygen atoms; R4and R5, independently from each other; are a hydrogen atom or a C1-6 alkyl group; or R3and R4or R3and R5, when taken together, form a C5-15 cycloalkyl, C5-15 cycloalkenyl, C4-14 heterocycloalkyl or C4-14 heterocycloalkenyl group, each optionally substituted with one or more of a C1-15 alkyl, Ci-s alkenyl C1-15 alkoxy, C3-15 cycloalkyl and / or C5-15 cycloalkenyl, each optionally substituted with one or more of a C1-8 alkyl, C1-8 alkoxy, carboxylic acid and / or C1-4 carboxylic ester group;wherein the heteroatom represents one or two oxygen atoms;R2represents a hydrogen atom; n is 1, 2, 3 or 4;X is an oxygen atom or a NR7group wherein R7is a hydrogen atom or a C1-6 alkyl group;R6is a hydrogen atom, a sodium, potassium or ammonium cation or a C1-16 hydrocarbon group, optionally containing one to nine oxygen atoms; at least one group among R4and R5is a C1-6 alkyl group; and provided that methyl 2-(8-methoxy-8-oxooctyl)thiazolidine-4-carboxylate, 2-(2,4,4- trimethylpentyl)thiazolidine-4-carboxylic acid, ethyl 2-(2,4,4-trimethylpentyl)thiazolidine-4- carboxylate, 2-(l-(4-isopropylphenyl)propan-2-yl)thiazolidine-4-carboxylic acid, 2-(2- phenylpropyl)thiazolidine-4-carboxylic acid and 2-(2,6-dimethylhept-5-en-l-yl)thiazolidine- 4-carboxylic acid are excluded.

15. A compound of formulain the form of any one of its stereoisomers or a mixture thereof, and wherein n is 1, 2, 3 or 4;X is an oxygen atom or a NR7group wherein R7is a hydrogen atom or a Ci-6 alkyl group;R6is a hydrogen atom, a sodium, potassium or ammonium cation or a Ci-i6 hydrocarbon group, optionally containing one to nine oxygen atoms;R8is a C3-9 hydrocarbon group optionally comprising one oxygen atom; R9and R10, independently from each other, are is a hydrogen atom or a methyl group; or R8and R10, when taken together, form a C5-8 cycloalkenyl group optionally substituted with one or more of a C1-6 alkyl or C2-6 alkenyl group.

16. The compound according to claim 14 or claim 15, wherein the compound of formula (I) is 2-(undecan-2-yl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(undecan-2- yl)thiazolidine-4-carboxylate, sodium 2-(undecan-2-yl)thiazolidine-4-carboxylate, 2-(6- methyl-5-hepten-2-yl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(6-methyl-5-hepten-2- yl)thiazolidine-4-carboxylate, 2-(3- and 4-(4-methyl-3-pentenyl)-3-cyclohexenyl)thiazolidine- 4-carboxylic acid, methyl or ethyl 2-(3- and 4-(4-methyl-3-pentenyl)-3- cyclohexenyl)thiazolidine-4-carboxylate, 2-(2-(4-methyl-3-cyclohexenyl)propyl)thiazolidine- 4-carboxylic acid, methyl or ethyl 2-(2-(4-methyl-3-cyclohexenyl)propyl)thiazolidine-4- carboxylate, 2-(non-3-en-l-yl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(non-3-en-l- yl)thiazolidine-4-carboxylate, 2-(undec-3-en-l-yl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(undec-3 -en- 1 -yl)thiazolidine-4-carboxylate, 2-(2-(4,4-dimethyl- 1 - cyclohexenyl)ethyl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(2-(4,4-dimethyl-l- cyclohexenyl)ethyl)thiazolidine-4-carboxylate, methyl or ethyl 2-(l-(4- isopropylphenyl)propan-2-yl)thiazolidine-4-carboxylate, methyl or ethyl 2-(2- phenylpropyl)thiazolidine-4-carboxylate, 2-(2,4-dimethylcyclohex-3-en-l-yl)thiazolidine-4- carboxylic acid, methyl or ethyl 2-(2,4-dimethylcyclohex-3-en-l-yl)thiazolidine-4- carboxylate, methyl or ethyl 2-nonylthiazolidine-4-carboxylate, 2-(4,8-dimethylnon-3-en-l- yl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(4,8-dimethylnon-3-en-l-yl)thiazolidine- 4-carboxylate, 2-(6-hydroxy-2,6-dimethylheptyl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(6-hydroxy-2,6-dimethylheptyl)thiazolidine-4-carboxylate, 2-(3-methyl-4-(4- methylphenyl)but-3-en-l-yl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(3-methyl-4-(4- methylphenyl)but-3-en-l-yl)thiazolidine-4-carboxylate, 2-(2-(l,l- or 3,3-dimethyl-2,3- dihydro-lH-inden-5- or 4-yl)ethyl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-(2-(l,l- or 3,3-dimethyl-2,3-dihydro-lH-inden-5- or 4-yl)ethyl)thiazolidine-4-carboxylate, 2-methyl- 2-(2-(2,6,6-trimethylcyclohex-l-en-l-yl)ethyl)thiazolidine-4-carboxylic acid, methyl or ethyl 2-methyl-2-(2-(2, 6, 6-trimethyl cyclohex- 1 -en- 1 -yl)ethyl)thiazolidine-4-carboxylate, 2-(4- hydroxyphenethyl)-2-methylthiazolidine-4-carboxylic acid, methyl or ethyl 2-(4- hydroxyphenethyl)-2-methylthiazolidine-4-carboxylate, 6-pentyl-l-thia-4- azaspiro[4.4]nonane-3-carboxylic acid, methyl or ethyl 6-pentyl-l-thia-4- azaspiro[4.4]nonane-3-carboxylate, 7-methyl-2H,4H-spiro[benzo[b][l,4]dioxepine-3,2'- thiazolidine]-4'-carboxylic acid, methyl or ethyl 7-methyl-2H,4H- spiro[benzo[b][l,4]dioxepine-3,2'-thiazolidine]-4'-carboxylate or oxybis(ethane-2,l-diyl)bis(2-(non-3-en-l-yl)thiazolidine-4-carboxylate) in the form of either one of its stereoisomers and / or a mixture thereof.

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