Alkyl Enol Ether Fragrance Procures

Abstract

The present invention relates to compounds of formula (I) as fragrance precursors. In particular, the present invention relates to a method for releasing compounds of formula (II), ketones of formula (III) and / or alcohols of formula (IV) by exposing the compounds of formula (I) to an environment in which they are oxidized. Furthermore, the present invention relates to perfuming compositions and perfumed consumer products comprising at least one compound of formula (I).

Description

Technical Field

[0001] The present invention relates to compounds of formula (I) as properfumes. In particular, the present invention relates to a method for releasing compounds of formula (II), ketones of formula (III) and / or alcohols of formula (IV) by exposing the compounds of formula (I) to an environment in which they are oxidized. Furthermore, the present invention relates to perfuming compositions and perfumed consumer products comprising at least one compound of formula (I). Background Art

[0002] The perfume (daily fragrance) industry is particularly interested in compositions or additives that can simultaneously prolong or enhance the perfuming effect of a mixture of several aromatics over a certain period of time. For standard perfume raw materials, it is particularly necessary to obtain lasting performance, which is too volatile or has very poor fragrance retention (substantivity) by itself, or is only deposited on the surface of the final application in small quantities. In addition, some perfume ingredients are unstable and need to be protected before use to prevent their slow degradation. Persistent perfumes are desirable for various applications, such as fine or functional perfumes or cosmetic preparations. The washing and softening of textiles is a specific field in which it is always necessary to make the effect of active substances, especially perfumes or perfuming compositions, effective for a period of time after washing, softening and drying. In fact, it is known that many active substances particularly suitable for this type of application lack persistence (tenacity) on clothing, or are not retained on clothing during rinsing, with the result that their perfuming effect is only experienced briefly rather than very strongly. Considering the importance of this type of application in the perfume industry, research in this field has been continued, especially in order to find new and more effective solutions to the above-mentioned problems. Summary of the invention

[0003] It has now surprisingly been found that the alkyl enol ether compounds according to the invention solve the above mentioned problems and are able to effectively release compounds as ketones of formula (II), formates of formula (III) and / or alcohols of formula (IV) while being stable in consumer products. BRIEF DESCRIPTION OF THE DRAWINGS

[0004] Figure 1 : Analysis of the concentration of (2-((2-methylundec-1-en-1-yl)oxy)ethyl)benzene, 1-ethoxydodec-1-ene, and 1-butoxydodec-1-ene in acidic solution versus time. DETAILED DESCRIPTION

[0005] Olfactory perception is a complex and dynamic process, and controlling the release profile of volatile aroma compounds can maximize the impact of fragrance formulations and enrich the sensory experience. Fragrance profragrances, such as the compounds of the present invention, increase the control range and persistence of the release profile of highly volatile fragrance raw materials (PRMs).

[0006] Without wishing to be bound by any particular theory, the compounds of the present invention may achieve their effect on the olfactory 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 point. In the present invention, the release of one, two or up to three PRMs is facilitated by oxidation when the fragrance pro-fragrance is exposed to oxygen in the ambient air.

[0007] In a first aspect, the present invention relates to a method for releasing a compound selected from the group consisting of:

[0008] a) Ketone of formula (II):

[0009]

[0010] Where R1 represents C 1-15 Alkyl, C 2-15 Alkenyl, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl or C 6-10 Aryl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, hydroxy, carboxylic acid and / or C 1-4 Carboxylate group;

[0011] R2 represents C 1-15 alkyl;

[0012] When R1 and R2 are combined together, C 5-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 4-14 Heterocycloalkyl or C 4-14 Heterocycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 2-15 Alkenyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, carboxylic acid, 4-methylcyclohex-3-en-1-yl and / or C 1-4 Carboxylate group,

[0013] wherein heteroatom represents one or more oxygen;

[0014] R4 each independently represents hydrogen or C 1-5 Alkyl; and

[0015] When R1 and R4 are combined together, C 3-15 Cycloalkyl or C 5-15 Cycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, carboxylic acid and / or C 1-4 Carboxylate groups;

[0016] b) Formic acid esters of formula (III):

[0017]

[0018] Where R3 represents hydrogen, C 1-15 Alkyl, C 2-15 Alkenyl, C 3-15 Cycloalkyl or C 5-15 Cycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, carboxylic acid and / or C 1-4 a carboxylate group; and

[0019] R4 has the same meaning as defined above; and

[0020] When R3 and R4 are combined together, C 3-15 Cycloalkyl or C5-15 Cycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, carboxylic acid and / or C 1-4 Carboxylate groups;

[0021] c) Alcohols of formula (IV):

[0022]

[0023] wherein R3 and R4 have the same meanings as defined above;

[0024] wherein at least one of the compounds of formula (II), (III) or (IV) is an active compound;

[0025] Wherein the precursor compound comprises a compound of formula (I):

[0026]

[0027] wherein R1, R2, R3 and R4 have the same meanings as defined above;

[0028] The process is carried out by exposing a precursor compound of formula (I) to an environment in which the compound is oxidized, ie ambient conditions.

[0029] The terms "active compound", "active volatile compound", "active volatile ketone, formate and / or alcohol" or similar terms refer herein to a ketone, formate and / or alcohol compound which is capable of bringing a benefit or effect to its surroundings. In particular, the "active compound" is selected from the group consisting of a perfuming ingredient, a flavoring ingredient, a malodor counteracting ingredient or an insect repellent or attractant ingredient. Therefore, to be considered an "active compound" a compound must have at least one property which makes it useful as a perfuming ingredient, as a malodor counteracting ingredient, a flavoring ingredient, and / or as an insect repellent or attractant.

[0030] The term "perfuming ingredient" is understood as a compound that is used as an active ingredient in a perfuming preparation or composition to impart a hedonic effect. In other words, to be considered a perfuming ingredient, this compound must be recognized by a person skilled in the art of perfumery as being able to impart or change the smell of the composition in an active or pleasant manner, rather than just having an odor. The term "flavoring ingredient" is understood as being able to impart a taste sensation to the pallet of a taster. The term "malodor counteracting ingredient" is understood as being able to reduce the perception of malodors (i.e., odors that are unpleasant or offensive to the human nose). The term "attractant or repellent" is understood as a compound that has a positive or negative effect on insects. Examples of attractant or repellent ingredients can be found in references or other works of similar nature, for example: AMEl-Sayed, The Pherobase 2005, http: / / www.pherobase.net.

[0031] According to the above and below mentioned embodiments of the present invention, when the active compound is a perfuming ingredient, i.e., a perfuming ketone, formates and / or alcohol, the method according to the present invention is particularly useful. "Perfuming ketones, formates and / or alcohols" are compounds used in the perfume industry, i.e., compounds used as active ingredients in perfuming preparations or compositions to impart a hedonic effect. In other words, to be considered as perfuming ketones, formates and / or alcohols, they must be recognized by the technicians in the field of perfumery as being able to impart or modify the smell of the composition in an active or pleasant manner, rather than just having a smell. Perfuming aldehydes, ketones, formates and / or alcohols can be natural or synthetic. In any case, many of these auxiliary ingredients are listed in references such as S. Arctander's work Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA or its updated version or other works of similar nature, as well as in the rich patent literature in the field of perfumery.

[0032] The term "perfuming ketones, formates and / or alcohols" as described herein is also referred to as "perfuming compounds".

[0033] In fact, the present invention proceeds in exactly the same way, regardless of the exact nature of the active ketone, formates or alcohols. It should therefore be understood that even though the invention will be further described hereinafter with specific reference to "perfuming compounds", the following embodiments are also applicable to other active ketones, formates and / or alcohols (i.e., for example, "perfuming" may be replaced by "flavoring", "malodor counteracting", "insect attractant" or "insect repellent").

[0034] The term "optionally" is to be understood as a group to be optionally substituted may or may not be substituted with a functional group. The term "one or more" is to be understood as substituted with 1 to 7, preferably 1 to 5 and more preferably 1 to 3 functional groups.

[0035] The terms "alkyl" and "alkenyl" are understood to include branched and straight chain alkyl and alkenyl groups. The terms "alkenyl", "cycloalkenyl" and "heterocycloalkenyl" are understood to include 1, 2 or 3 olefinic double bonds, preferably 1 or 2 olefinic double bonds. The terms "cycloalkyl", "cycloalkenyl", "heterocycloalkyl" and "heterocycloalkenyl" are understood to include monocyclic or fused, spiro and / or bridged bicyclic or tricyclic cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl, preferably monocyclic cycloalkyl, cycloalkenyl, heterocycloalkyl and heterocycloalkenyl.

[0036] The term "aryl" is understood to include any group containing at least one aromatic group, for example phenyl, indenyl, indanyl, tetrahydronaphthyl or naphthyl.

[0037] The term "C 1-15 "Alkoxy" is understood to mean an RO-group, in which R is a linear, branched, cyclic or aliphatic C 1-15 alkyl or alkenyl.

[0038] According to any one of the above embodiments of the present invention, the compound (I) is C 16 -C 28 Compounds, especially C 18 -C 26 Compounds, and even more particularly C 19 -C 24 Compound.

[0039] In a preferred embodiment, in the case where "when R1 and R4 are taken together" and / or "when R3 and R4 are taken together" form a cycloalkenyl, it is understood that the olefinic double bond is not adjacent to the carbon to which R1 and R4 or R3 and R4 are attached, respectively. In a preferred embodiment, in the case where an alkoxy group is substituted on the alkenyl group, the alkoxy group cannot be adjacent to the olefinic double bond of the alkenyl group to form an enol ether.

[0040] According to any embodiment of the present invention, R1 represents C 1-10 Alkyl, C 2-10 Alkenyl, C 3-11 Cycloalkyl or C 5-11 Cycloalkenyl, each of which is optionally substituted with one or more C 1-4 Alkyl, C 1-4 Alkoxy, C 3-8 Cycloalkyl, C 5-8Cycloalkenyl, C6 aryl and / or C6 aryloxy, each of which may be optionally substituted with one or more C 1-4 Alkyl or C 1-4 Alkoxy, carboxylic acid and / or C 1-4 Carboxylic acid esters.

[0041] According to any embodiment, R1 represents C 1-10 Alkyl, C 2-10 Alkenyl or C 3-11 Cycloalkyl, each of which is optionally substituted with one or more C 1-4 Alkyl, C 1-4 Alkoxy, C 3-8 Cycloalkyl, C 5-8 Cycloalkenyl, C6 aryl and / or C6 aryloxy, each of which may be optionally substituted with one or more C 1-4 Alkyl or C 1-4 Alkoxy.

[0042] According to any embodiment, R1 represents C 1-10 Alkyl, optionally substituted with C 5-7 Cycloalkyl, C 5-7 Cycloalkenyl and / or C6 aryl, each of which may be optionally substituted with one or more C 1-4 Alkyl and / or C 1-4 Preferably, R1 represents C 1-10 Alkyl, optionally substituted with C 5-7 Cycloalkyl, C 5-7 Cycloalkenyl and / or C6 aryl, each of these substituents may be optionally substituted with one or more methyl and / or methoxy groups.

[0043] According to any embodiment, R2 represents C 1-10 In a particular embodiment, R2 represents C 1-5 In a particular embodiment, R2 represents C 1-3 The alkyl group is preferably a methyl group or an ethyl group.

[0044] According to any embodiment, when R1 and R2 are combined together, they form C 5-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 4-15 Heterocycloalkyl or C 4-15 Heterocycloalkenyl, each of which is optionally substituted with one or more C 1-7 Alkyl, C 2-8 Alkenyl, C 1-5 Alkoxy, C 3-8 Cycloalkyl, C 5-8 Cycloalkenyl or C6 aryl, each of which may be optionally substituted with one or more C 1-5Alkyl, C 1-5 Alkoxy, carboxylic acid, 4-methylcyclohex-3-en-1-yl and / or C 1-4 A carboxylate group wherein the heteroatom represents one or more oxygen.

[0045] According to a particular embodiment, when R1 and R2 are combined together, they form C 5-15 Cycloalkyl or C 5-15 Cycloalkenyl, each optionally substituted with 1 to 4 C 1-7 Alkyl or C 2-8 Alkenyl.

[0046] According to any embodiment, when R1 and R2 are combined together, they form C 5-11 Cycloalkyl, C 5-11 Cycloalkenyl, C 4-11 Heterocycloalkyl or C 4-11 Heterocycloalkenyl, each of which is optionally substituted with one or more C 1-7 Alkyl, C 2-8 Alkenyl C 1-5 Alkoxy, C 3-8 Cycloalkyl, C 5-8 Cycloalkenyl or C6 aryl, each of which may be optionally substituted with one or more C 1-5 Alkyl, C 1-5 Alkoxy, carboxylic acid, 4-methylcyclohex-3-en-1-yl and / or C 1-4 A carboxylate group wherein the heteroatom represents one or more oxygen.

[0047] In a particular embodiment, when R1 and R2 are combined together, they form C 5-11 Cycloalkyl, C 5-11 Cycloalkenyl, C 4-11 Heterocycloalkyl or C 4-11 Heterocycloalkenyl, each of which is optionally substituted with one or more C 1-5 Alkyl, C 1-5 Alkoxy, C 3-8 Cycloalkyl, C 5-8 Cycloalkenyl or C6 aryl, each of which may be optionally substituted with one or more C 1-5 Alkyl, C 1-5 Alkoxy, carboxylic acid and / or C 1-4 A carboxylate group wherein the heteroatom represents one or more oxygen.

[0048] According to any embodiment, when R1 and R2 are combined together, they form C 5-7 Cycloalkyl, C 5-7 Cycloalkenyl, C 5-7 Heterocycloalkyl or C 5-8 Heterocycloalkenyl, each of which is optionally substituted with one or more C1-7 Alkyl, C 2-6 Alkenyl, C 1-4 Alkoxy, C 5-7 Cycloalkyl, C 5-7 Cycloalkenyl or C6 aryl, each of which may be optionally substituted with one or more C 1-3 Alkyl, C 1-3 Alkoxy, carboxylic acid, 4-methylcyclohex-3-en-1-yl and / or C 1-3 A carboxylate group wherein the heteroatom represents one or more oxygen.

[0049] In a particular embodiment, when R1 and R2 are combined together, they form C 5-7 Cycloalkyl, C 5-7 Cycloalkenyl, C 5-7 Heterocycloalkyl or C 5-8 Heterocycloalkenyl, each of which is optionally substituted with one or more C 1-4 Alkyl, C 1-4 Alkoxy, C 5-7 Cycloalkyl, C 5-7 Cycloalkenyl or C6 aryl, each of which may be optionally substituted with one or more C 1-3 Alkyl, C 1-3 Alkoxy, carboxylic acid and / or C 1-3 A carboxylate group wherein the heteroatom represents one or more oxygen.

[0050] According to any embodiment, when R1 and R2 are combined together, they form C 5-7 Cycloalkyl or C 5-7 Cycloalkenyl, each of which is optionally substituted with one or more C 1-7 Alkyl, C 2-6 Alkenyl or C 1-4 Alkoxy.

[0051] According to any embodiment, when R1 and R2 are combined together, they form C 5-7 Cycloalkyl or C 5-7 Cycloalkenyl, each of which is optionally substituted with one or more C 1-4 Alkyl, C 2-6 Alkenyl or C 1-4 Alkoxy.

[0052] According to any embodiment, when R1 and R2 are combined together, they form C 10-15 Cycloalkyl or C 10-15 Cycloalkenyl, each of which is optionally substituted with a methyl group, or when R1 and R2 are combined together, form a C 5-6 Cycloalkyl or C 5-6 Cycloalkenyl, each optionally substituted with 1 to 3 C 1-7 Alkyl, C2-6 Alkenyl or C 1-4 Alkoxy.

[0053] According to any embodiment, R4 each independently represents a hydrogen atom or C 1-5 In a particular embodiment, R4 each independently represents a hydrogen atom or a C 1-3 In a particular embodiment, R4 each independently represents a hydrogen atom, and only one R4 represents a C 1-3 In a particular embodiment, R4 each independently represents a hydrogen atom, and only one R4 represents a C 1-2 In a preferred embodiment, R4 each represents a hydrogen atom.

[0054] According to any embodiment, when R1 and R4 (adjacent to R1) are combined together to form C 3-11 Cycloalkyl or C 5-11 Cycloalkenyl, each of which is optionally substituted with one or more C 1-5 Alkyl, C 1-5 Alkoxy, C 3-7 Cycloalkyl, C 5-7 Cycloalkenyl and / or C6 aryl, each of which may be optionally substituted with one or more C 1-4 Alkyl or C 1-4 Alkoxy.

[0055] According to any embodiment, when R1 and R2 are combined together, they form C 3-11 Cycloalkyl or C 5-11 Cycloalkenyl, each of which is optionally substituted with one or more C 1-3 Alkyl or C 1-3 Alkoxy.

[0056] According to any embodiment, when R1 and R2 are combined together, they form C 3-11 Cycloalkyl, optionally substituted with one or more C 1-3 Alkyl or C 1-3 Alkoxy.

[0057] According to any embodiment, R3 represents C 1-10 Alkyl, C 2-10 Alkenyl, C 3-15 Cycloalkyl or C 5-11 Cycloalkenyl, each of which is optionally substituted with one or more C 1-5 Alkyl, C 1-5 Alkoxy, C 3-8 Cycloalkyl, C 5-8 Cycloalkenyl, C6 aryl and / or C6 aryloxy, each of which may be optionally substituted with one or more C 1-5 Alkyl or C1-5 Alkoxy.

[0058] According to any embodiment, R3 represents C 1-10 Alkyl, C 3-10 Alkenyl, C 4-15 Cycloalkyl or C 5-11 Cycloalkenyl, each of which is optionally substituted with one or more C 1-4 Alkyl, C 1-4 Alkoxy, C 5-6 Cycloalkyl, C 5-6 Cycloalkenyl C6 aryl and / or C6 aryloxy, each of which may be optionally substituted with one or more C 1-3 Alkyl or C 1-3 Alkoxy.

[0059] According to any embodiment, R3 represents C 1-10 Alkyl, C 3-10 Alkenyl or C 5-15 Cycloalkyl, each of which is optionally substituted with one or more C 1-4 Alkyl, C6 aryl and / or C6 aryloxy.

[0060] According to any embodiment, R3 represents benzyl, phenoxymethyl, heptyl, pentyl, 4-methylhex-5-en-1-yl or pent-5-en-1-yl.

[0061] According to any embodiment, when R3 and R4 (adjacent to R3) are combined together, C 3-12 Cycloalkyl or C 5-11 Cycloalkenyl, each of which is optionally substituted with one or more C 1-5 Alkyl, C 1-5 Alkoxy, C 3-7 Cycloalkyl, C 5-7 Cycloalkenyl and / or C6 aryl, each of which may be optionally substituted with one or more C 1-4 Alkyl or C 1-4 Alkoxy.

[0062] According to any embodiment, when R3 and R4 are combined together, C 3-12 Cycloalkyl or C 5-11 Cycloalkenyl, each of which is optionally substituted with one or more C 1-3 Alkyl or C 1-3 Alkoxy.

[0063] According to any embodiment, when R3 and R4 are combined together, C 3-12 Cycloalkyl, optionally substituted with one or more C 1-3 Alkyl or C 1-3 Alkoxy.

[0064] In a particular embodiment, the ketone of formula (II), the formic ester of formula (III) and / or the active alcohol of formula (IV) is a perfuming ingredient. For a person skilled in the art it is also obvious that the compounds according to the invention are inherently volatile compounds.

[0065] The ketone, formates and / or alcohols may advantageously be characterized by a vapor pressure higher than 1.0 Pa, calculated using the software EPIwin v.3.10 (2000, available from the U.S. Environmental Protection Agency). According to another embodiment, the vapor pressure of the ketone, formates and / or alcohol may be higher than 5.0, or even higher than 7.0 Pa.

[0066] In one embodiment, the compound of formula (I) is non-volatile. The compound of formula (I) can advantageously be characterized by a vapor pressure below 0.01 Pa, calculated using the software EPIwin v.3.10 (2000, available from the U.S. Environmental Protection Agency). According to a preferred embodiment, the vapor pressure is below 0.001 Pa.

[0067] In a particular embodiment, the ketone of formula (II) is selected from the group consisting of 2-butanone, 2-pentanone, 2-hexanone, 2-heptanone, 2-octanone, 2-nonanone, 2-undecanone, 2-tridecanone, 2-pentadecanone, 3-heptanone, 3-octanone, 4-nonanone, 5-undecanone, 5-methyl-3-heptanone, 6-methyl-5-hepten-2-one, 2,6-dimethyl-7-octen-4-one (dihydrotaglenone), 2-(sec-butyl)cyclohexan-1-one, 2-(tert-butyl)cyclohexan-1-one, 4-(tert-butyl)cyclohexan-1-one, 4-(tert-butyl)cyclohexan-1-one, Hexan-1-one, 5-isopropyl-2-methylcyclohexan-1-one, 2-isopropyl-5-methylcyclohexan-1-one, 2,2,6-trimethylcyclohexan-1-one, 2,2,4-trimethylbicyclo[3.1.1]heptan-3-one, thujanone, 2-ethyl-4,4-dimethylcyclohexan-1-one, 1,7,7-trimethylbicyclo[2.2.1]heptan-2-one, 7-methyloctahydro-1,4-methylnaphthalene-6(2H)-one, thujopsan-4-one, 1,3,3-trimethylbicyclo[2.2.1] Heptan-2-one, 4-phenyl-2-butanone, 4-(4-hydroxyphenyl)-2-butanone, 4-(4-methoxyphenyl)-2-butanone, zingerone, 4-(1,3-benzodioxol-5-yl)-2-butanone, 2-cyclohexyl-4-methyl-2-pentanone, 1-(4-methyl-1-phenoxy)-2-propanone, 2,2,6-trimethylcyclohexanone, 4-(2,6,6-trimethylcyclohex-2-en-1-yl)butan-2-one (dihydro-α-ionone), 4-(2,6,6-trimethylcyclohexanone)- Hex-1-en-1-yl)butan-2-one (dihydro-β-ionone), (5-E / Z)-6,10-dimethylundec-5,9-dien-2-one, cyclopentadecanone, (Z)-cycloheptadecan-9-en-1-one, 3-methylcyclopentadecan-1-one, (Z)-cyclopentadecan-4-en-1-one, 3-methylcyclopentadecan-5-en-1-one, (4E / Z,8E / Z)-cyclododeca-4,8-dien-1-one, 7-methyl-2H-benzo[b][1,4]dioxepin-3(4H)-one, 7-propyl- 2H-Benzo[b][1,4]dioxepin-3(4H)-one, 1-(5-propylbenzo[d][1,3]dioxol-2-yl)ethan-1-one, 4,4a,6,7,8,8a-hexahydro-1,4-methylnaphthalene-5(1H)-one, 2-pentylcyclopent-1-one, 2-heptylcyclopent-1-one, 2-(hex-5-en-1-yl)cyclopent-1-one, 2,2,5-trimethyl-5-pentylcyclopent-1-one, 2-(3-oxo-2-pentylcyclopentyl)acetate, Iso-E-Super, Jasmine 1-(5-isopropyl-2-methylcyclohex-2-en-1-yl)propan-1-one, 2,2,7,9-tetramethylspiro[5.5]undec-7-en-1-one), 4-ethyl-8-methyloctahydronaphthalen-1(2H)-one, isolongifolianone, 1-(3,3-dimethylcyclohexyl)ethan-1-one, 2,6,6-trimethylcycloheptan-1-one, 3,6,8,8-tetramethylhexahydro-1H-3a,7-methylazulene-5(4H)-one and 2-(2-(4-(methylcyclohex-3-en-1-yl)propyl)cyclopentan-1-one.

[0068] In a more specific embodiment, the ketone of formula (II) is selected from the group consisting of cyclododeca-4,8-dien-1-one, 2-(2-(4-methylcyclohex-3-en-1-yl)propyl)cyclopentan-1-one, 2-isopropyl-5-methylcyclohexan-1-one, 7-methyloctahydro-1,4-methylnaphthalen-6(2H)-one, 2-(hex-5-en-1-yl)cyclopentan-1-one, 2-ethyl-4,4-dimethylcyclohexan-1-one, 2-nonanone, 2-decanone, 2-undecanone, 4-phenyl-2- butanone, 4-(4-methoxyphenyl)-2-butanone, 4-(tert-pentyl)cyclohexan-1-one, 4-(1,3-benzodioxol-5-yl)-2-butanone, 4-(2,6,6-trimethylcyclohex-2-en-1-yl)butan-2-one (dihydro-α-ionone), 4-(2,6,6-trimethylcyclohex-1-en-1-yl)butan-2-one, 2-pentylcyclopentan-1-one, 2-heptylcyclopentan-1-one, 3-methylcyclopentadecan-1-one, cyclopentadecanone and 2,2,6-trimethylcyclohexanone.

[0069] In a particular embodiment, the formic acid ester of formula (III) is selected from the group consisting of methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, pentyl formate, 2-methylbutyl formate, 3-methylbutyl formate, butyl-2-formate, 2-methylpropyl formate, cyclohexyl formate, hexyl formate, heptyl formate, octyl formate, nonyl formate, decyl formate, 3-octyl formate, benzyl formate, 3,7-dimethyloctyl formate, -6-enyl ester, 3,7-dimethyloct-7-enyl formate, cinnamyl formate, 4-methoxybenzyl formate, (E)-3,7-dimethyloct-2,6-dien-1-yl formate, (Z)-3,7-dimethyloct-2,6-dien-1-yl formate, 2-hexenyl formate, 3-hexenyl formate, 3,5,5-trimethylhexyl formate, 2-phenylethyl formate, 2-(phenoxy)ethyl formate, 3-phenylpropyl formate, methyl 3-methylbut-2-enyl formate, bornyl formate, isobornyl formate, 2-methyl-5-(prop-1-en-2-yl)cyclohex-2-en-1-yl formate, cedryl formate, cyclododecyl formate, decahydronaphthalene-2-yl formate, menthyl formate, 1-phenylethyl formate, 5-methyl-2-(prop-1-en-2-yl)cyclohexyl formate, 3a,4,5,6,7,7a-hexahydro-1H-4 ,7-methanoinden-5-yl ester, 3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-6-yl formate, 1-(3,3-dimethylcyclohexyl)ethyl formate, 2-methyl-1-phenylpropan-2-yl formate, 3,7-dimethyloct-1,6-dien-3-yl formate, 2,6-dimethyloct-7-en-2-ol formate, 1-((2-(tert-butyl)cyclohexyl)oxy)butan-2-yl formate.

[0070] In a more specific embodiment, the formic acid ester of formula (III) is selected from the group consisting of: 2-phenylethyl formate, 3-hexenyl formate, octyl formate, decyl formate, 3,7-dimethyloct-6-en-1-yl formate, 3,7-dimethyloct-7-enyl formate, 2-phenoxyethyl formate, 1-((1RS,6SR)-2,2,6-trimethylcyclohexyl)hex-3-yl formate, hexyl formate, benzyl formate, oct ... 3-yl formate, (1RS,2SR,5RS)-2-isopropyl-5-methylcyclohexyl formate, cyclododecyl formate, 1-(3,3-dimethylcyclohexyl)ethyl formate, 1-((2-(tert-butyl)cyclohexyl)oxy)butan-2-yl formate, 2,6-dimethyloct-7-en-2-yl formate, 3,7-dimethyloct-3-yl formate, 2-methyl-1-phenylpropan-2-yl formate, 2,6-dimethylhept-2-yl formate.

[0071] In a particular embodiment, the alcohol of formula (IV) is selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, pentanol, 2-methylbutanol, 3-methylbutanol, butan-2-ol, 2-methylpropanol, cyclohexanol, hexanol, heptanol, octanol, nonanol, decanol, 2-hexanol, 3-octanol, benzyl alcohol, 9-decen-1-ol, 3,7-dimethyloct-6-en-1-ol, 3,7-dimethyloct-7-en-1-ol, cinnamyl alcohol, 4-methoxybenzyl alcohol, (E)-3,7-dimethyloct-2,6-dien-1-ol, (Z)-3,7-dimethyloct-2,6-dien-1-ol cyclohex-2-en-1-ol, cedrol, cyclododecanol, decahydronaphthalen-2-ol, menthol, 1-phenylethanol, 5-methyl-2-(prop-1-en-2-yl)cyclohex-1-ol, 3-Methyl-5-phenylpentan-1-ol, (4-isopropylcyclohexyl)methanol, (E)-4-methyl-3-decen-5-ol, 2-pentyl-1-cyclopentanol, 5-ethyl-2-nonanol, 4-(tert-butyl)cyclohexan-1-ol, 2-methoxy-4-propylcyclohexan-1-ol, 3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-5-ol, 3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-6-ol, 1-(3,3-dimethylcyclohexyl)ethanol, 2-methyl-1-phenylpropan-2-ol, 3,7-dimethyloctan-1,6- Dien-3-ol, 2,6-dimethyloct-7-en-2-ol, 2,6-dimethyloct-2-ol, 4-cyclohexyl-2-methyl-2-butanol, (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol, 1-((2-(tert-butyl)cyclohexyl)oxy)butan-2-ol, 1-((1RS,6SR)-2,2,6-trimethylcyclohexyl)hexan-3-ol, 2,6-dimethyl-2-heptanol, 2-methyl-4-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-1-ol, 2-methyl-1-phenylpropan-2-ol.

[0072] In a more preferred embodiment, the alcohol of formula (IV) is selected from the group consisting of: 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 3-octanol, 1-decanol, benzyl alcohol, 3,7-dimethyloct-6-en-1-ol, 3,7-dimethyloct-7-en-1-ol, 3-hexen-1-ol, 2-phenylethanol, 2-(phenoxy)ethanol, 9-decen-1-ol, 2,6-dimethyloct-7-en-2-ol, (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol, 3-hexen-1-ol and cyclododecanol.

[0073] According to any embodiment, the compound of formula (I) is selected from the group consisting of: (2-((2-methylundec-1-en-1-yl)oxy)ethyl)benzene, (2-((2-methylundec-1-en-1-yl)oxy)ethoxy)benzene, (3-methyl-4-phenethoxybut-3-en-1-yl)benzene, 1-methoxy-4-(2-methyl-3-phenethoxyallyl)benzene, (2-((2-methyl-4-(2,6,6-trimethylcyclohex-1-en-1-yl)but-1-en-1-yl)oxy)ethyl)benzene, (2-((2,2,6-trimethylcyclohexylidene)methoxy)ethyl)benzene, 2-methyl-1-(octyloxy)benzene )undec-1-ene, (3-methyl-4-(octyloxy)but-3-en-1-yl)benzene, 1-methoxy-4-(3-methyl-4-phenylethoxybut-3-en-1-yl)benzene, 2-methyl-1-(oct-3-yloxy)undec-1-ene, (3-methyl-4-(oct-3-yloxy)but-3-en-1-yl)benzene, 1-methoxy-4-(2-methyl-3-(oct-3-yloxy)allyl)benzene, 1,3,3-trimethyl-2-(3-methyl-4-(oct-3-yloxy)but-3-en-1-yl)cyclohex-1-ene, ((2-methylundec-1-en-1-yl)oxy)cyclododecane, 1-((2,6 1-(((Z)-hex-3-en-1-en)oxy)-2-methylundec-1-ene, (2-((2-methyldec-1-en-1-yl)oxy)ethyl)benzene, 1-((3,7-dimethyloct-6-en-1-yl)oxy)-2-methylundec-1-ene, (2-((2-ethylhex-1-en-1-yl)oxy)ethyl)benzene, (phenethoxymethylene)cyclopentadecane, (2-((4-(tert-pentyl)cyclohexylidene)methoxy)ethyl)benzene, 9-(phenethoxymethylene)cyclododeca-1,5-diene, (1SR, 4RS, 4aS R,8aRS)-6-methyl-7-(phenethoxymethylene)decahydro-1,4-methylnaphthalene, (2-(((2RS,5SR)-2-isopropyl-5-methylcyclohexylidene)methoxy)ethyl)benzene, (2-((2-(2-((R)-4-methylcyclohex-3-en-1-yl)propyl)cyclopentylidene)methoxy)ethyl)benzene, (2-((2-pentylcyclopentylidene)methoxy)ethyl)benzene, (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene, (2-((2-ethyl-4,4-dimethylcyclohexylidene)methoxy)ethyl)benzene, (2-((2-ethyl-4-methylhex-1-en-1-yl)oxy)ethyl)benzene. In particular, the compound of formula (I) is selected from (2-((2-methylundec-1-en-1-yl)oxy)ethyl)benzene and 1-methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene.

[0074] In a particular embodiment, at least two of the compounds of formula (II), (III) and (IV) are active compounds.

[0075] In a more specific embodiment, the compounds of formula (II), (III) and (IV) are active compounds.

[0076] According to any embodiment, the ketone of formula (II), the formate of formula (III) and the alcohol of formula (IV) are released from the precursor compound of formula (I) by oxidation of the precursor compound of formula (I) under ambient conditions. Even, the precursor compound of formula (I) is oxidized under ambient conditions and without any catalyst. For the sake of clarity, the normal meaning understood by those skilled in the art is represented by the expression "ambient conditions" or similar terms, that is, oxidation occurs at room temperature in air and atmospheric pressure. In other words, the environment in which the compound is oxidized is air. It can be understood from this that the compound of formula (I) is oxidized in ambient air. In particular, it should be understood that the compound of formula (I) does not need a pure oxygen environment, heat or catalyst to oxidize.

[0077] Without wishing to be bound by any particular theory, the rate at which the precursor compound of formula (I) is oxidized may be greater than, equal to, or slower than the rate at which the respective ketone of formula (II), the respective formates of formula (III), or the respective alcohols of formula (IV) evaporate.

[0078] In some embodiments, the rate at which the precursor compound of formula (I) is oxidized, and thereby the rate at which the respective ketone of formula (II), the respective formate of formula (III), or the respective alcohol of formula (IV) is released, enhances or prolongs the diffusion effect and / or the perceived characteristic aroma of at least one active ketone of formula (II), at least one active formate of formula (III), and / or at least one active alcohol of formula (IV) as defined above.

[0079] In one embodiment, 100% of the compound of formula (I) is oxidized within a period of 24 to 48 hours in ambient air. Alternatively, 90% of the compound of formula (I) is oxidized within a period of 24 to 48 hours in ambient air. Alternatively, 80% of the compound of formula (I) is oxidized within a period of 24 to 48 hours in ambient air. Alternatively, 70% of the compound of formula (I) is oxidized within a period of 24 to 48 hours in ambient air. Alternatively, 60% of the compound of formula (I) is oxidized within a period of 24 to 48 hours in ambient air. Alternatively, 50% of the compound of formula (I) is oxidized within a period of 24 to 48 hours in ambient air. Alternatively, 40% of the compound of formula (I) is oxidized within a period of 24 to 48 hours in ambient air. Alternatively, 30% of the compound of formula (I) is oxidized within a period of 24 to 48 hours in ambient air. Alternatively, 20% of the compound of formula (I) is oxidized in ambient air over a period of 24 to 48 hours. Alternatively, 10% of the compound of formula (I) is oxidized in ambient air over a period of 24 to 48 hours. Alternatively, 9% of the compound of formula (I) is oxidized in ambient air over a period of 24 to 48 hours. Alternatively, 8% of the compound of formula (I) is oxidized in ambient air over a period of 24 to 48 hours. Alternatively, 7% of the compound of formula (I) is oxidized in ambient air over a period of 24 to 48 hours. Alternatively, 6% of the compound of formula (I) is oxidized in ambient air over a period of 24 to 48 hours. Alternatively, 5% of the compound of formula (I) is oxidized in ambient air over a period of 24 to 48 hours. Alternatively, 4% of the compound of formula (I) is oxidized in ambient air over a period of 24 to 48 hours. Alternatively, 3% of the compound of formula (I) is oxidized in ambient air over a period of 24 to 48 hours. Alternatively, 2% of the compound of formula (I) is oxidized in ambient air over a period of 24 to 48 hours. Alternatively, 1% of the compound of formula (I) is oxidized in ambient air over a period of 24 to 48 hours.

[0080] In a specific embodiment, the compound of formula (I) is encapsulated. At least one compound of formula (I) can be encapsulated in microcapsules. In a preferred embodiment, at least one compound of formula (I) is encapsulated in core-shell microcapsules, wherein the compound of formula (I) is contained in a core surrounded by a shell. The shell of the microcapsule protects the compound of formula (I) from environmental influences. The shell is made of a material capable of releasing the compound of formula (I) and / or the active compound of formula (II), formula (III) and / or formula (IV). In a preferred embodiment, the shell is made of a material capable of releasing the compound of formula (I) and / or the active compound of formula (II), formula (III) and / or formula (IV) when the shell is broken and / or by diffusion through the shell. The method for preparing the microcapsules is well known to those skilled in the art.

[0081] The nature of the polymer shell from the microcapsules of the present invention can vary. As non-limiting examples, the shell can be aminoplast-based, polyurea-based or polyurethane-based. The shell can also be composite, i.e., organic-inorganic, such as a composite shell composed of at least two cross-linked inorganic particles, or a shell produced by the hydrolysis and condensation reaction of a polyalkoxysilane macromonomer composition.

[0082] According to one embodiment, the shell comprises an aminoplast copolymer, such as melamine-formaldehyde or urea-formaldehyde or crosslinked melamine-formaldehyde or melamine-glyoxal.

[0083] According to another embodiment, the shell is polyurea-based, made from, for example but not limited to, isocyanate-based monomers and amine-containing crosslinking agents such as guanidine carbonate and / or guanazole. Preferred polyurea-based microcapsules comprise: a polyurea wall, which is a polymeric reaction product between at least one polyisocyanate containing at least two isocyanate functional groups and at least one reactant selected from amines (e.g., water-soluble guanidine salts and guanidine); a colloidal stabilizer or emulsifier; and an encapsulated fragrance. However, the use of amines can be omitted.

[0084] According to a specific embodiment, the colloidal stabilizer comprises an aqueous solution of 0.1% to 0.4% polyvinyl alcohol, 0.6% to 1% of a cationic copolymer of vinyl pyrrolidone and quaternized vinyl imidazole (all percentages are defined relative to the total weight of the colloidal stabilizer). According to another embodiment, the emulsifier is an anionic or amphiphilic biopolymer, preferably selected from gum arabic, soy protein, gelatin, sodium caseinate and mixtures thereof.

[0085] According to another embodiment, the shell is polyurethane based, made from, for example but not limited to, polyisocyanates and polyols, polyamides, polyesters, and the like.

[0086] The preparation of aqueous dispersion / slurry of core-shell microcapsules is well known to those skilled in the art. In one form, the microcapsule wall material may include any suitable resin and especially include melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, etc. Suitable resins include the reaction product of aldehydes and amines, and 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, urea-resorcinol and mixtures thereof. Suitable manufacturing materials may be obtained from one or more of Solutia Inc. (St Louis, Missouri USA), Cytec Industries (West Paterson, New Jersey U.S.A.), Sigma-Aldrich (St.Louis, Missouri USA).

[0087] According to a specific embodiment, the core-shell microcapsules are formaldehyde-free capsules. A typical method for preparing an aminoplast-free formaldehyde-free microcapsule slurry comprises the following steps: 1) preparing an oligomeric composition comprising the reaction product of the following ingredients, or an oligomeric composition obtained by reacting the following ingredients together:

[0088] a) a polyamine component in the form of melamine or in the form of a mixture of melamine and at least one C1-C4 compound containing two NH2 functions;

[0089] b) Glyoxal, C 4-6 The aldehyde component is in the form of a mixture of 2,2-dialkoxyacetaldehyde and optionally glyoxylate, the glyoxal / C 4-6 The molar ratio of 2,2-dialkoxyethanol is 1 / 1 to 10 / 1; and

[0090] c) protonic acid catalyst;

[0091] 2) preparing an oil-in-water dispersion, wherein the droplet size is 1 to 600 μm, and comprising:

[0092] i.Oil;

[0093] ii. Water medium

[0094] iii. at least one oligomeric composition as obtained in step 1;

[0095] iv. at least one cross-linking agent selected from the group consisting of:

[0096] A) C4-C 12Aromatic or aliphatic di- or triisocyanates and their biuret, triuret, trimer, trimethylolpropane adducts and mixtures thereof; and / or

[0097] B) a di- or tri-oxirane compound of the formula

[0098] A-(Oxiran-2-ylmethyl) n

[0099] wherein n represents 2 or 3, and l represents a C2-C6 group optionally containing 2 to 6 nitrogen and / or oxygen atoms;

[0100] v. Optionally, a C1-C4 compound comprising two NH2 functional groups;

[0101] 3) heating the dispersion;

[0102] 4) Cooling the dispersion.

[0103] This method is described in more detail in WO 2013 / 068255, the contents of which are incorporated herein by reference.

[0104] According to another embodiment, the shell of the microcapsule is polyurea-based or polyurethane-based. Examples of methods for preparing polyurea-based and polyurethane-based microcapsule slurries are described, for example, in WO2007 / 004166, EP2300146, EP2579976, the contents of which are also incorporated herein by reference. A method generally used to prepare a polyurea-based or polyurethane-based microcapsule slurry comprises the following steps:

[0105] a) dissolving at least one polyisocyanate having at least two isocyanate groups in oil to form an oil phase;

[0106] b) preparing an aqueous solution of an emulsifier or a colloid stabilizer to form an aqueous phase;

[0107] c) adding the oil phase to the water phase to form an oil-in-water dispersion, wherein the average droplet size is 1 to 500 μm, preferably 5 to 50 μm;

[0108] d) applying conditions sufficient to initiate interfacial polymerization and form microcapsules in the form of a slurry.

[0109] In a particular embodiment, the encapsulation of the compound of formula (I) can provide an environment within the capsule in which all or a portion of the compound of formula (I) can be oxidized, thereby releasing the individual ketones of formula (II), the individual formates of formula (III), or the individual alcohols of formula (IV) into the capsule. In a preferred embodiment, the shell of the microcapsule can act as a permeation barrier to prevent the individual ketones of formula (II), the individual formates of formula (III), or the individual alcohols of formula (IV) from leaking out of the capsule.

[0110] In a second aspect, the present invention relates to a method or process for imparting, enhancing, improving or modifying the odor characteristics of a perfuming composition, the air surrounding the perfuming composition, a surface or a perfumed article, comprising adding to the composition, the air or the article an effective amount of at least one compound of formula (I) as defined above or contacting or treating the surface with an effective amount of at least one compound of formula (I) as defined above. As used herein, the term "surface" may refer to the user's skin, hair, fabric or hard surface to which a perfume composition comprising or containing at least one compound of formula (I) is applied.

[0111] In a third aspect, the invention relates to a method for intensifying or prolonging the diffusion of the characteristic aroma of at least one active ketone of formula (II), at least one active formate of formula (III) and / or at least one active alcohol of formula (IV) as defined above on a surface or in the air surrounding a perfuming composition, wherein the surface or the air is treated with at least one compound (I) as defined above or with a composition or preparation containing at least one compound (I) under conditions allowing the release over time of at least one active ketone of formula (II), at least one active formate of formula (III) and / or at least one active alcohol of formula (IV).

[0112] In a fourth aspect, the invention relates to a perfuming composition comprising:

[0113] i) at least one compound of formula (I) as defined above;

[0114] ii) an ingredient selected from the group consisting of a fragrance carrier and a fragrance base; and

[0115] iii) optionally, at least one flavor adjuvant.

[0116] By "perfume carrier" it is meant here a material which is practically neutral from a perfume point of view, ie which does not significantly alter the organoleptic properties of the perfuming ingredient. The carrier may be liquid or solid.

[0117] As liquid carrier, there may be cited, as non-limiting examples, emulsifying systems, i.e. solvents and surfactant systems, or solvents commonly used in perfumes. A detailed description of the properties and types of solvents commonly used in perfumes is not exhaustive. However, there may be cited, as non-limiting examples, solvents such as butylene glycol or propylene glycol, glycerol, dipropylene glycol and its monoethers, 1,2,3-propanetriol triacetate, dimethyl glutarate, dimethyl adipate, 1,3-diacetoxyprop-2-yl acetate, diethyl phthalate, isopropyl myristate, benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethanol, triethyl citrate or mixtures thereof, which are the most commonly used. For compositions comprising both a perfume carrier and a perfume base, in addition to those described in detail above, other suitable perfume carriers may also be ethanol, a water / ethanol mixture, limonene or other terpenes, isoparaffins, such as those sold under the trademark Those known as (source: Exxon Chemical), or glycol ethers and glycol ether esters, such as those sold under the trademark Those known as castor oil (source: Dow Chemical Company), or hydrogenated castor oil, such as those sold under the trademark RH 40 Those known per se (source: BASF).

[0118] Solid carrier refers to a kind of material, and some composition of perfuming composition or perfuming composition can be combined with it chemically or physically.Usually, use such solid carrier to stabilize composition, or control the evaporation rate of composition or some composition.Solid carrier is what uses in this field at present, and those skilled in the art know how to reach the desired effect.Yet, as the non-limiting example of solid carrier, can enumerate absorption gum or polymer or inorganic material, for example porous polymer, cyclodextrin, wood-based material, organic or inorganic gel, clay, gypsum, talcum or zeolite.

[0119] As other non-limiting examples of solid carriers, encapsulating materials can be cited. Examples of such materials may include wall-forming materials and plasticizing materials, such as monosaccharides, disaccharides or trisaccharides, natural or modified starch, hydrocolloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, proteins or pectins, or in references such as H.Scherz, Hydrokolloide: Stabilisatoren, Dickungs- und Geliermittel in Lebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie, Materials listed in Behr's Verlag GmbH & Co., Hamburg, 1996. Encapsulation is a process well known to the person skilled in the art and may be performed, for example, using techniques such as spray drying, agglomeration or extrusion; or consist of coating encapsulation including coacervation and complex coacervation techniques.

[0120] As non-limiting examples of solid supports, one may in particular cite core-shell capsules using resins of the aminoplast, polyamide, polyester, polyurea or polyurethane type or mixtures thereof (all said resins being well known to a person skilled in the art), by a phase separation process initiated using techniques such as polymerization, interfacial polymerization, coacervation or these techniques together (all said techniques having been described in the prior art), and optionally in the presence of polymeric stabilizers or cationic copolymers.

[0121] The resins may be produced by polycondensation of aldehydes such as formaldehyde, 2,2-dimethoxyacetaldehyde, glyoxal, glyoxylic acid or glycolaldehyde and mixtures thereof with amines such as urea, benzoguanamine, glycoluryl, melamine, methylolmelamine, methylated methylolmelamine, guanazole, and the like and mixtures thereof. Alternatively, preformed resins may be used, such as those sold under the trademark (Source: Cytec Technology Corp.), (Source: Cytec Technology Corp.), or (Source: BASF) Those that are commercially available.

[0122] Other resins are obtained by mixing a polyol such as glycerol with a polyisocyanate such as a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate or xylylene diisocyanate, or a biuret of hexamethylene diisocyanate, or a trimer of xylylene diisocyanate and trimethylolpropane (known under the trade name Known sources: those produced by the polycondensation of xylylene diisocyanate (source: Mitsui Chemicals), wherein the trimer of xylylene diisocyanate with trimethylolpropane and the biuret of hexamethylene diisocyanate.

[0123] Some research literature related to the encapsulation of spices by condensation of amino resins, i.e. melamine-based resins, with aldehydes includes articles such as Acta Polymerica, 1989, vol. 40, pages 243, 325 and 683 and 1990, vol. 41, page 91 by K. Dietrich et al. These articles have described various parameters that affect the preparation of such core-shell microcapsules according to prior art methods, which are also further detailed and exemplified in the patent literature. US 4'396'670 of Wiggins Teape Group Limited is a relevant early example of the latter. Since then, many other authors have enriched the literature in this field, and it is not possible to cover all the published progress here, but general knowledge of encapsulation technology is very important. More recent targeted publications also involve suitable uses of such microcapsules, such as the articles by HY Lee et al. Journal of Microencapsulation, 2002, vol. 19, pages 559-569, international patent publications WO01 / 41915 or et al., Chimia, 2011, vol. 65, pages 177-181.

[0124] The term "perfume base" is to be understood as a composition comprising at least one perfuming co-ingredient.

[0125] Perfuming co-ingredients are not compounds according to the invention. Furthermore, the term "perfuming co-ingredient" is to be understood as a compound which is used in a perfuming preparation or composition to impart a hedonic effect. In other words, to be considered a perfuming co-ingredient such a co-ingredient must be recognized by a person skilled in the art as being able to impart or modify the odor of a composition in an active or pleasant manner, rather than merely possessing an odor.

[0126] The nature and types of perfuming co-ingredients present in the base do not warrant a more detailed description here, which is in no way exhaustive, and a person skilled in the art will be able to choose them according to his general knowledge and according to the intended use or application and the desired organoleptic effect. In general, these perfuming co-ingredients belong to different chemical classes, such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen- or sulfur-containing heterocyclic compounds and essential oils, and may be of natural or synthetic origin.

[0127] In particular, one may cite perfuming co-ingredients known to have similar olfactory notes, for example:

[0128] In particular, one may cite the perfuming auxiliary ingredients usually used in perfume formulations, for example:

[0129] - Aldehyde aroma components: decanal, dodecanal, 2-methylundecane, 10-undecenal, octanal and / or nonenal;

[0130] - aromatic herbal ingredients: eucalyptus oil, camphor, eucalyptol, menthol and / or alpha-pinene;

[0131] - balsamic ingredients: coumarin, ethyl vanillin and / or vanillin;

[0132] - Citrus aroma ingredients: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpenes, limonene, 1-p-menthen-8-yl acetate and / or 1,4(8)-p-menthenadiene;

[0133] -Floral fragrance ingredients: methyl dihydrojasmonate, linalool, citronellol, phenylethyl alcohol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexyl cinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, β-ionone, methyl 2-(methylamino)benzoate, (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, tricyclodecenyl acetate, geraniol, p-menthen-1-en-8-ol, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, methyl homo-dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol, tricyclodecenyl propionate, geranyl acetate, tetrahydrolinalool, cis-7-p-menthol, (S)-2-(1,1-dimethylpropoxy)propyl propionate, 2-methoxynaphthalene, 2,2,2-trichloro-1-phenylethyl acetate, 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, amyl cinnamaldehyde, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, tricyclodecenyl isobutyrate and / or a mixture of methylionone isomers;

[0134] -Fruit aroma ingredients: γ-undecalactone, 4-decanoic acid ethyl ester, hexyl acetate, 2-methylbutyric acid ethyl ester, γ-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-acetate and / or diethyl 1,4-cyclohexanedicarboxylate;

[0135] - Green aroma ingredients: 2,4-dimethyl-3-cyclohexene-1-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styroyl acetate, (2-methylbutoxy) allyl acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z)-3-hexen-1-ol and / or 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one;

[0136] - Musk ingredients: 1,4-dioxa-5,17-cycloheptadecanedione, pentadecanolide, 3-methyl-5-cyclopentadecan-1-one, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[G]-2-benzopyran, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropyl propionate, pentadecanolide and / or (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methyl propionate;

[0137] - Woody components: 1-(octahydro-2,3,8,8-tetramethyl-2-naphthyl)-1-ethanone, patchouli oil, terpene fraction of patchouli oil, (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, methyl cedryl ketone, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol, 1-(2,3,8,8-tetramethyl-1,2,3,4,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one and / or isobornyl acetate;

[0138] -Other ingredients (e.g. ambery, powdery, spicy or watery): dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan and any of its stereoisomers, piperonal, anisaldehyde, eugenol, cinnamaldehyde, clove oil, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal and / or 3-(3-isopropyl-1-phenyl)butanal.

[0139] The perfume base according to the invention may not be limited to the above mentioned perfuming co-ingredients, and many other such co-ingredients are anyway listed in references such as S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA or its updated editions, or other works of similar nature, as well as a large number of patent documents in the field of perfumery. It should also be understood that the co-ingredients may also be compounds known to release various types of perfuming compounds in a controlled manner.

[0140] The term "perfume adjuvant" is understood as an ingredient capable of imparting additional additional benefits such as color, specific light fastness, chemical stability, etc. A detailed description of the nature and types of adjuvants commonly used in perfuming compositions is not exhaustive, but it must be mentioned that said ingredients are well known to the person skilled in the art. As specific non-limiting examples the following may be cited: viscous agents (e.g. surfactants, thickeners, gelling and / or rheology modifiers), stabilizers (e.g. preservatives, antioxidants, heat / light or buffers or chelating agents, such as BHT), colorants (e.g. dyes and / or pigments), preservatives (e.g. antibacterial or antimicrobial or antifungal or anti-irritant), abrasives, skin cooling agents, fixatives, insect repellents, ointments, vitamins and mixtures thereof.

[0141] It will be appreciated that a person skilled in the art is fully capable of designing the best formulation for the desired effect simply by applying standard knowledge in the field and mixing the above-mentioned components of the perfuming composition by trial and error.

[0142] Besides perfuming compositions comprising at least one compound according to the invention, at least one perfume carrier, at least one perfume base and optionally at least one perfume adjuvant, the compositions according to the invention consisting of at least one compound of formula (I) according to the invention and at least one perfume carrier also represent a particular embodiment of the present invention.

[0143] It is useful here to mention that the possibility of having more than one compound of the invention or other precursors of similar type in the above compositions is important, since this enables the perfumer to prepare blends or fragrances having odor notes of different compounds of the invention, thereby creating new building blocks for creative purposes.

[0144] For the sake of clarity, it is also to be understood that any mixture resulting directly from a chemical synthesis in which the composition of matter of the invention is used as starting material, intermediate or end product, such as a reaction medium without sufficient purification, cannot be considered as a perfuming composition according to the invention, as long as said mixture does not provide the compounds of the invention in a form suitable for use in perfumery. Therefore, unpurified reaction mixtures are generally excluded from the present invention, unless otherwise stated.

[0145] Furthermore, the compounds according to the invention can also be used advantageously in all areas of modern perfumery, ie fine perfumery or functional perfumery, in order to actively impart or modify the odor of consumer products to which the compounds (I) are added.

[0146] Therefore, in a fifth aspect, the present invention also relates to a perfumed consumer product comprising at least one compound of formula (I) as defined above or a perfuming composition as defined above.

[0147] For the sake of clarity, it must be mentioned that a "perfumed consumer product" is understood to be a consumer product that delivers at least one pleasant perfuming effect to the surface to which it is applied (e.g. skin, hair, fabric or hard surface). In other words, a perfumed consumer product according to the invention is a perfumed consumer product comprising a functional formulation and optionally additional benefit agents corresponding to a desired consumer product (e.g. a conditioner, detergent or air freshener), and an olfactory effective amount of at least one compound of the invention. For the sake of clarity, a perfumed consumer product is a non-edible product.

[0148] The nature and types of ingredients of the perfumed consumer product do not warrant a more detailed description here, which is in any case non-exhaustive, the skilled person being able to choose them on the basis of his general knowledge and according to the characteristics of the product in question and the desired effect.

[0149] 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.

[0150] Non-limiting examples of suitable perfumed consumer products include perfumes, such as fine perfumes, splashes or eau de perfums, colognes or shaving lotions or aftershaves; fabric care products, such as liquid or solid detergents, fabric softeners, liquid or solid fragrance enhancers, fabric refreshers, ironing water, paper, bleach, carpet cleaners, curtain care products; body care products, such as hair care products (e.g. shampoos, coloring preparations or hair sprays, color care products, hair styling products, dental care products), disinfectants, intimate care products; cosmetic preparations (e.g. skin creams or lotions, vanishing creams, or body deodorants (deodorants) or antiperspirants (e.g. sprays or roll-ons), depilatories, suntan preparations, sunscreens or aftersun products , nail products, skin cleansing products, cosmetics); or skin care products (e.g. soaps, bath mousses, bath oils or shower gels, or hygiene products or foot / hand care products); air care products, such as air fresheners or "ready-to-use" powder air fresheners, which can be used in domestic spaces (rooms, refrigerators, cupboards, shoes or cars) and / or public spaces (lobbies, hotels, shopping malls, etc.); or home care products, such as mildew removers, furniture care agents, wipes, dishwashing detergents or detergents for hard surfaces (e.g. floors, bathrooms, sanitary ware or window cleaning); leather care products; car care products, such as polishes, waxes or plastic cleaners.

[0151] Typical examples of fabric detergent or softener compositions that can incorporate the compounds of the present invention are described in WO 97 / 34986 or U.S. Pat. Nos. 4,137,180 and 5,236,615 or EP 799 885. Other typical detergent and softener compositions that can be used are described in, for example, Ullmann's Encyclopedia of Industrial Chemistry, vol. 20, Wiley-VCH, Weinheim, p. 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.

[0152] The proportions in which the compounds according to the invention can be incorporated into the various preparations or compositions described above vary within wide ranges of values. These values ​​depend on the nature of the preparation to be perfumed and the desired organoleptic effect, as well as on the nature of the co-ingredients in a given base, when the compounds according to the invention are mixed with perfuming co-ingredients, solvents or additives commonly used in the art.

[0153] For example, based on the weight of the composition into which it is incorporated, the typical concentration of the compounds of the present invention is 0.001% to 10% by weight, or even more. When these compounds are used directly for the fragrance or flavoring of the above-mentioned various consumer products, concentrations lower than these, such as 0.001% to 5% by weight, can be used.

[0154] In a sixth aspect, the present invention relates to a compound of formula (I):

[0155]

[0156] Where R1 represents C 1-15 Alkyl, C 2-15 Alkenyl, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl or C 6-10 Aryl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, carboxylic acid and / or C 1-4 Carboxylate group;

[0157] R2 represents C 1-15 alkyl;

[0158] When R1 and R2 are combined together, C 5-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 4-14 Heterocycloalkyl or C 4-14 Heterocycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 2-15 Alkenyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, carboxylic acid, 4-methylcyclohex-3-en-1-yl and / or C 1-4 Carboxylate group,

[0159] wherein heteroatom represents one or more oxygen atoms;

[0160] R3 represents C 1-15 Alkyl, C 3-15 Alkenyl, C 3-15 Cycloalkyl or C 5-15 Cycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, carboxylic acid and / or C 1-4 Carboxylate groups;

[0161] R4 each independently represents hydrogen or C 1-5 alkyl;

[0162] When R1 and R4 are combined together, C 3-15 Cycloalkyl or C5-15 Cycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, carboxylic acid and / or C 1-4 Carboxylate groups;

[0163] When R3 and R4 are combined together, C 3-15 Cycloalkyl or C 5-15 Cycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, carboxylic acid and / or C 1-4 a carboxylate group; and

[0164] The compound of formula (I) is C 16 -C 28 Compounds,

[0165] The conditions are:

[0166] - When R1 is methyl, then R2 is not methyl or ethyl,

[0167] - When R1 is ethyl, then R2 is not ethyl,

[0168] - when R3 is an unsubstituted methyl group, then R4 is not a hydrogen atom or a methyl group,

[0169] - when R3 is an unsubstituted ethyl group, then R4 is not a hydrogen atom,

[0170] The condition is to exclude the following compounds:

[0171] (((3,7-dimethyloct-1,6-dien-3-yl)oxy)methylene)cyclohexane,

[0172] 3-(((2-ethylhex-1-en-1-yl)oxy)methyl]heptane,

[0173] 4-(((7-methyloctyl)oxy)methylene)cyclohex-1-ene,

[0174] 4-((Dodecyloxy)methylene)cyclohex-1-ene,

[0175] (4-((4-phenylbutoxy)methylene)cyclohexyl)benzene,

[0176] 1-((2-ethylhex-1-en-1-yl)oxy)octane,

[0177] 1-((2-ethylhex-1-en-1-yl)oxy)dodecane,

[0178] 2-Ethylhexenyl lauryl ether,

[0179] 2-Ethylhexenyl octyl ether,

[0180] 1-(2'-ethylhexyloxy)-2-ethyl-1,3-hexadiene,

[0181] 1-((2-methylpent-1-en-1-yl)oxy)dodecane,

[0182] 3-(Cyclohexylenemethoxy)-1,5,5-trimethylcyclohex-1-ene,

[0183] (3-(Benzyloxy)-2-methylallyl)benzene, and

[0184] 4-(4-(Allyloxy)-3-methylbut-3-en-1-yl)-1,2-dimethoxybenzene.

[0185] Exemplary embodiments of the compounds of formula (I) are described above.

[0186] In a preferred embodiment, the following moiety of formula (I) corresponds to a ketone of formula (II) as defined above.

[0187]

[0188] In a preferred embodiment, the following part of formula (I) corresponds to the alcohol of formula (IV) as defined above.

[0189]

[0190] In another form, the present invention also relates to microcapsules comprising at least one compound of formula (I). In a preferred embodiment, at least one compound of formula (I) is encapsulated in a core-shell microcapsule, wherein the compound of formula (I) is contained in a core surrounded by a shell. The shell of the microcapsule protects the compound of formula (I) from environmental influences. The shell is made of a material capable of releasing the compound of formula (I) and / or the active compound of formula (II), formula (III) and / or formula (IV). In a preferred embodiment, the shell is made of a material capable of releasing the compound of formula (I) and / or the active compound of formula (II), formula (III) and / or formula (IV) when the shell is broken and / or by diffusion through the shell. The method for preparing the microcapsules is well known to those skilled in the art.

[0191] In another aspect, the present invention also relates to the use of a precursor compound for releasing a compound selected from the group consisting of:

[0192] a) Ketone of formula (II):

[0193]

[0194] Where R1 represents C 1-15 Alkyl, C 2-15 Alkenyl, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl or C 6-10 Aryl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, hydroxyl, carboxylic acid and / or C 1-4 Carboxylate group;

[0195] R2 represents C 1-15 alkyl;

[0196] When R1 and R2 are combined together, C 5-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 4-14 Heterocycloalkyl or C 4-14 Heterocycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 2-15 Alkenyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, carboxylic acid, 4-methylcyclohex-3-en-1-yl and / or C 1-4 Carboxylate group,

[0197] wherein heteroatom represents one or more oxygen;

[0198] R4 each independently represents hydrogen or C 1-5 Alkyl; and

[0199] When R1 and R4 are combined together, C 3-15 Cycloalkyl or C 5-15 Cycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, carboxylic acid and / or C 1-4 Carboxylate groups;

[0200] b) Formic acid esters of formula (III):

[0201]

[0202] Where R3 represents hydrogen, C 1-15 Alkyl, C 2-15 Alkenyl, C 3-15 Cycloalkyl or C 5-15 Cycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, carboxylic acid and / or C 1-4 a carboxylate group; and

[0203] R4 has the same meaning as defined above; and

[0204] When R3 and R4 are combined together, C 3-15 Cycloalkyl or C 5-15Cycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, carboxylic acid and / or C 1-4 Carboxylate groups;

[0205] c) Alcohols of formula (IV):

[0206]

[0207] wherein R3 and R4 have the same meanings as defined above;

[0208] wherein at least one of the compounds of formula (II), (III) or (IV) is an active compound;

[0209] Wherein the precursor compound comprises a compound of formula (I):

[0210]

[0211] wherein R1, R2, R3 and R4 have the same meanings as defined above,

[0212] This use is accomplished by exposing the precursor compound to an environment in which the compound is oxidized.

[0213] In another aspect, the invention relates to the use of at least one compound of formula (I) as defined above for imparting, enhancing, improving or modifying the odor characteristics of a perfuming composition, the air surrounding the perfuming composition, a surface or a perfumed article, comprising adding an effective amount of at least one compound of formula (I) as defined above 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. As used herein, the term "surface" may refer to the user's skin, hair, fabric or hard surface to which a perfume composition comprising or containing at least one compound of formula (I) is applied.

[0214] In another aspect, the present invention relates to the use of at least one compound of formula (I) as defined above for enhancing or prolonging the diffusion effect and / or perception of the characteristic aroma of at least one active ketone of formula (II), at least one active formate of formula (III) and / or at least one active alcohol of formula (IV) as defined above on a surface, wherein the surface is treated with at least one compound (I) as defined above or with a composition or preparation containing at least one compound (I) under conditions allowing the release of at least one active ketone of formula (II), at least one active formate of formula (III) and / or at least one active alcohol of formula (IV) over time.

[0215] Example

[0216] 1. Preparation of Compounds

[0217] The following compounds have been prepared and characterized. Unless otherwise stated, only mass spectral data (EI, 70 eV), major fragment ions and relative abundances and NMR data of the E-isomer (usually the major isomer) are provided. CDCl3 is used as solvent to record NMR spectra. Chemical shift δ is expressed in ppm relative to TMS as a standard, and coupling constant J is expressed in Hz.

[0218] Examples 1 to 6.

[0219] Dimethyl acetal (35 mmol), alcohol (70 mmol) and KHSO4 (48 mg, 0.35 mmol) were added to a 25 ml round bottom flask equipped with a distillation head and a nitrogen bubbler. The mixture was heated (oil bath at 150°C) while distilling off the released methanol (vapor temperature 64°C) until the vapor temperature dropped (40-60 minutes), indicating that most of the methanol had been removed. The mixture was placed under vacuum (300 mTorr) and heated (180-190°C oil bath) for 2-3 hours while distilling off the released alcohol from the reaction flask. After the addition of Na2CO3 (0.5 g), the enol ether was isolated from the reaction flask by vacuum distillation or by silica gel flash chromatography followed by Kugelrohr distillation.

[0220] Example 1. (2-((2-methylundec-1-en-1-yl)oxy)ethyl)benzene:

[0221] Starting from 2-methylundecanal and the dimethyl acetal of 2-phenylethanol, the title compound was isolated by distillation (bp 130°C, 30 mTorr) as a colorless oil in 91% yield (E / Z=59:41).

[0222] 1H NMR (CDCl3, 500 MHz, E-isomer): δ 0.88 (t, J = 7.0 Hz, 3H), 1.19-1.39 (m, 14H), 1.57 (s, 3H), 1.85 (t, J = 7.5 Hz, 2H), 2.91 (t, J = 7.3 Hz, 2H), 3.86 (t, J = 7.3 Hz, 2H), 5.81 (s, 1H), 7.17-7.30 (m, 5H).

[0223] Example 2. (2-((2-methylundec-1-en-1-yl)oxy)ethoxy)benzene:

[0224] Starting from 2-methylundecanal and the dimethyl acetal of 2-phenoxyethanol, the title compound was isolated by distillation (bp 128-130° C., 25 mTorr) as a colorless oil in 90% yield (E / Z=60:40).

[0225] 1 H NMR (CDCl3, 600 MHz, E-isomer): δ 0.88 (t, J = 7.0 Hz, 3H), 1.19-1.39 (m, 14H), 1.58 (s, 3H), 1.85 (t, J = 7.4 Hz, 2H), 4.00 (t, J = 5.0 Hz, 2H), 4.12 (t, J = 5.0 Hz, 2H), 5.89 (s, 1H), 6.89-6.96 (m, 3H), 7.24-7.30 (m, 2H).

[0226] Example 3. (3-methyl-4-phenethoxybut-3-en-1-yl)benzene:

[0227] Starting from 2-methyl-4-phenylbutyraldehyde and the dimethyl acetal of 2-phenylethanol, the title compound was isolated by distillation (bp 135° C., 30 mTorr) as a colorless oil in 83% yield (E / Z=52:48).

[0228] 1 H NMR (CDCl3, 600 MHz, E-isomer): δ 1.64 (d, J = 1.2 Hz, 3H), 2.16 (t, J = 7.9 Hz 2H), 2.66 (t, J = 7.9 Hz, 2H), 2.83 (t, J = 7.2 Hz, 2H), 3.81 (t, J = 7.2 Hz, 2H), 5.76 (q, J = 1.2 Hz, 1H), 7.11-7.30 (m, 10H).

[0229] Example 4. 1-methoxy-4-(2-methyl-3-phenylethoxyallyl)benzene:

[0230] Starting from 3-(4-methoxyphenyl)-2-methylpropanal and dimethyl acetal of 2-phenylethanol, the title compound was isolated by distillation (bp 155-158° C., 30 mTorr) as a colorless oil in 77% yield (E / Z=56:44).

[0231] 1 H NMR (CDCl3, 600 MHz, E-isomer): δ1.5 (s, 3H), 2.92 (t, J = 7.2 Hz, 2H), 3.09 (s, 2H), 3.76 (s, 3H), 3.90 (t, J = 7.2 Hz, 2H), 5.91 (s, 1H), 6.79-6.82 (m, 2H), 7.03-7.08 (m, 2H), 7.18-7.31 (m, 5H).

[0232] Example 5. (2-((2-methyl-4-(2,6,6-trimethylcyclohex-1-en-1-yl)but-1-en-1-yl)oxy)ethyl)benzene:

[0233] Starting from 2-methyl-4-(2,6,6-trimethylcyclohex-1-en-1-yl)butanal and dimethyl acetal of 2-phenylethanol, the title compound was isolated as a colorless oil by flash chromatography on silica gel (hexane / EtOAc, 98:3) followed by Kugelrohr distillation (180°C, 30 mTorr) in a yield of 74% (E / Z=45:55).

[0234] 1 H NMR (CDCl3, 600 MHz, E-isomer): δ 0.98 (s, 3H), 1.00 (s, 3H), 1.39-1.44 (m, 2H), 1.54-1.59 (m, 2H), 1.60 (s, 3H), 1.64 (s, 3H), 1.86-194 (m, 3H), 1.99-2.06 (m, 2H), 2.07-2.13 (m, 1H), 2.93 (t, J = 7.1 Hz, 2H), 3.88 (t, J = 7.1 Hz, 2H), 5.86 (s, 1H), 7.18-7.24 (m, 3H), 7.25-7.31 (m, 2H).

[0235] Example 6. (2-((2,2,6-trimethylcyclohexylene)methoxy)ethyl)benzene

[0236] Starting from 2,2,6-trimethylcyclohexane-1-carbaldehyde and dimethyl acetal of 2-phenylethanol, the title compound was isolated by silica gel flash chromatography (hexane / EtOAc, 98:2) followed by Kugelrohr distillation (130-150°C, 40 mTorr) as a light amber oil in 70% yield (E / Z=76:24).

[0237] 1 H NMR (CDCl3, 500 MHz, E-isomer): δ 1.00 (s, 3H), 1.07 (s, 3H), 1.11 (d, J = 7.4 Hz, 3H), 1.19-1.77 (m, 6H), 2.90 (t, J = 7.0 Hz, 2H), 2.91-3.05 (m, 1H), 3.87 (t, J = 7.0 Hz, 2H), 5.83 (s, 1H), 7.17-7.31 (m, 5H).

[0238] Examples 7 to 8.

[0239] A solution of aldehyde (30-25 mmol), 1-octanol (2.5 eq.) and TsOH (0.02 eq.) in toluene (100 ml) was heated to reflux for 2-3 hours. The reaction water was removed using a Dean-Stark trap. The reaction mixture was diluted with EtOAc and then washed with saturated NaHCO3 and water. The organic phase was dried over Na2SO4, filtered and concentrated to give the crude dioctyl acetal. This material was mixed with KHSO4 (0.02 eq.) and heated at 180°C for 1-2 hours using a Kugelrohr distillation apparatus under vacuum (35 Torr). The remaining residue was then Kugelrohr distilled to give the enol ether (typical conditions, 140-170°C, 50 mTorr).

[0240] Example 7. 2-Methyl-1-(octyloxy)undec-1-ene:

[0241] Starting from 2-methylundecanal, the title compound was isolated as a colorless liquid in a yield of 53% (E / Z=50:50).

[0242] 1 H NMR (CDCl3, 500 MHz, E-isomer): δ 0.88 (t, J = 6.9 Hz, 6H), 1.20-1.40 (m, 24H), 1.54-1.64 (m, 2H), 1.58 (s, 3H), 1.85 (t, J = 7.4 Hz, 2H), 3.65 (t, J = 6.7 Hz, 2H), 5.80 (s, 1H).

[0243] Example 8. (3-methyl-4-(octyloxy)but-3-en-1-yl)benzene:

[0244] Starting from 2-methyl-4-phenylbutyraldehyde, the title compound was isolated as a colorless liquid in a yield of 57% (E / Z=58:42).

[0245] 1 H NMR (CDCl3, 600 MHz, E-isomer): δ 0.88 (t, J = 6.9 Hz, 3H), 1.21-1.38 (m, 10H), 1.51-1.58 (m, 2H), 1.66 (s, 3H), 2.16 (t, J = 8.0 Hz, 2H), 2.67 (t, J = 8.0 Hz, 2H), 3.61 (t, J = 6.7 Hz, 2H), 5.77 (s, 1H), 7.13-7.28 (m, 5H).

[0246] Example 9. 1-methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene:

[0247] Methoxymethyltriphenylphosphonium chloride (17.7 g, 51.7 mmol) and 4-(4-methoxyphenyl)butan-2-one (6.12 g, 34.3 mmol) were added to 150 ml of toluene. Potassium tert-butoxide (6.18 g, 55.1 mmol) was added to the stirred slurry 4 times at 15-minute intervals. The mixture was stirred for another 4 hours, during which it became a light yellow homogeneous solution. It was then poured into 200 ml of water and extracted with ether (3×100 mL). The organic phases were combined, dried over MgSO4, filtered and concentrated. The residue was subjected to silica gel flash chromatography (hexane / CH2Cl2 100:0→75:25) to obtain 4.06 g (19.7 mmol) of the methyl enol ether product. In a round-bottom flask (25 mL) equipped with a distillation head and a nitrogen bubbler, this material (3.8 g, 18.4 mmol) was mixed with 2-phenylethanol (4.5 g, 36.8 mmol) and KHSO (0.027 g, 0.198 mmol). The mixture was heated at 150° C. for 1 hour, and free methanol was distilled from the mixture. The mixture was then placed under vacuum (300 mTorr) and heated at 190° C. for 2 hours, while excess 2-phenylethanol was distilled from the flask. NaCO (0.3 g) was added to the flask, and the title compound (4.46 g, 15.1 mmol) was isolated by distillation (bp 170° C., 30 mTorr) as a colorless oil in 82% yield (E / Z=57:43).

[0248] 1H NMR (CDCl3, 600 MHz, E-isomer): δ 1.63 (d, J = 1.2 Hz, 3H), 2.13 (br t, J = 7.9 Hz, 2H), 2.61 (m, 2H), 2.86 (t, J = 7.2 Hz, 2H), 3.76 (s, 3H), 3.84 (t, J = 7.2 Hz, 2H), 5.77 (q, J = 1.2 Hz, 1H), 6.80 (d, J = 8.6 Hz, 2H), 7.07 (d, J = 8.6 Hz, 2H), 7.17-7.31 (m, 5H).

[0249] Examples 10 to 14.

[0250] A toluene solution (100 ml) of aldehyde (30-25 mmol), 3-octanol (2.5 eq.) and TsOH (0.02 eq.) was heated to reflux for 3-4 hours. The reaction water was removed using a Dean-Stark trap. The reaction mixture was diluted with EtOAc and then washed with saturated NaHCO3 and water. The organic phase was dried over Na2SO4, filtered and concentrated. The residue was subjected to Kugelrohr distillation to first remove excess 3-octanol (typical conditions, 90°C, 50 mTorr) and then to obtain the enol ether (typical conditions, 140-170°C, 50 mTorr).

[0251] Example 10. 2-Methyl-1-(oct-3-yloxy)undec-1-ene:

[0252] Starting from 2-methylundecanal, the title compound was isolated as a colorless oil in a yield of 46% (E / Z=61:39).

[0253] 1 H NMR (CDCl3, 500 MHz, E-isomer): δ 0.88 (t, J = 7.1 Hz, 3H), 0.89 (t, J = 7.1 Hz, 3H), 0.90 (t, J = 7.3 Hz, 3H), 1.20-1.56 (m, 24H), 1.58 (s, 3H), 1.85 (t, J = 7.4 Hz, 2H), 3.42 (quintet, J = 5.7 Hz, 1H), 5.81 (s, 1H).

[0254] Example 11. (3-methyl-4-(oct-3-yloxy)but-3-en-1-yl)benzene:

[0255] Starting from 2-methyl-4-phenylbutyraldehyde, the title compound was isolated as a colorless oil in a yield of 56% (E / Z=58:42).

[0256] 1H NMR (CDCl3, 600 MHz, E-isomer): δ 0.86 (t, J = 7.4 Hz, 3H), 0.89 (t, J = 7.0 Hz, 3H), 1.21-1.53 ​​(m, 10H), 1.65 (s, 3H), 2.16 (t, J = 7.9 Hz, 2H), 2.67 (t, J = 7.9 Hz, 2H), 3.37 (quintet, J = 6.1 Hz, 1H), 5.76 (s, 1H), 7.12-7.29 (m, 5H).

[0257] Example 12. 1-methoxy-4-(2-methyl-3-(oct-3-yloxy)allyl)benzene:

[0258] Starting from 3-(4-methoxyphenyl)-2-methylpropanal, the title compound was isolated as a colorless oil in a yield of 53% (E / Z=59:41).

[0259] 1 H NMR (CDCl3, 500 MHz, E-isomer): δ 0.89 (t, J = 7.0 Hz, 3H), 0.92 (t, J = 7.4 Hz, 3H), 1.24-1.36 (m, 5H), 1.36-1.61 (m, 5H), 1.51 (s, 3H), 3.10 (s, 2H), 3.49 (quintet, J = 6.3 Hz, 1H), 3.77 (s, 3H), 5.95 (s, 1H), 6.80-6.82 (m 2H), 7.06-7.09 (m, 2H).

[0260] Example 13. 1,3,3-trimethyl-2-(3-methyl-4-(oct-3-yloxy)but-3-en-1-yl)cyclohex-1-ene:

[0261] Starting from 2,2,6-trimethylcyclohexane-1-carbaldehyde, the title compound was isolated after two consecutive Kugelrohr distillations as a colorless oil in a yield of 38% (E / Z=50:50).

[0262] 1 H NMR (CDCl3, 500 MHz, E-isomer): δ 0.86-0.92 (overlapping triplet, 6H), 0.99 (s, 3H), 1.02 (s, 3H), 1.22-1.60 (m, 14H), 1.60 (s, 3H), 1.65 (s, 3H), 1.87-1.94 (m, 3H), 2.00-2.13 (m, 3H), 3.44 (quintet, J = 6.0 Hz, 1H), 5.86 (s, 1H).

[0263] Example 14. ((2-methylundec-1-en-1-yl)oxy)cyclododecane:

[0264] A mixture of 2-methylundecanal (4.17 g, 22.6 mmol), cyclododecanol (4.24 g, 23 mmol), TsOH (0.08 g, 0.421 mmol) and toluene (50 mL) was heated to reflux for 2 hours while removing the reaction water using a Dean-Stark trap. After the mixture was cooled, it was diluted with EtOAc and washed with saturated NaHCO3 and saturated NaCl. The organic phase was dried over Na2SO4, filtered and concentrated. The residue was Kugelrohr distilled (160-180°C, 50 mTorr) to give 2.54 g of the title compound (7.24 mmol, 32% yield) as a colorless oil (E / Z=55:45).

[0265] 1 H NMR (CDCl3, 500 MHz, E-isomer): δ 0.88 (t, J = 6.9 Hz, 3H), 1.20-1.45 (m, 32H), 1.46-1.59 (m, 2H), 1.57 (s, 3H), 1.59-1.70 (m, 2H), 1.85 (t, J = 7.4 Hz, 2H), 3.67 (quintet, J = 7.5 Hz, 1H) 5.82 (s, 1H).

[0266] Example 15. 1-((2,6-dimethyloct-7-en-2-yl)oxy)-2-methylundec-1-ene:

[0267] A hexane solution (100 ml) of 2-methylundecane (14.9 g, 81 mmol), dihydromyrcenol (25.4 g, 163 mmol) and TsOH (0.31 g, 1.63 mmol) was heated to reflux for 5 hours while removing the reaction water with a Dean-Stark trap. The mixture was diluted with additional hexane and washed with saturated NaHCO3 and brine. The organic phase was dried over Na2SO4, filtered and concentrated. After addition of Na2CO3 (1 g), the residue was short-path distilled (bp 138°C, 30 mTorr) to give 2.2 g of the title compound (6.82 mmol, 8% yield) (E / Z=61:39) as a colorless oil (E / Z=61:39).

[0268] 1H NMR (CDCl3, 600 MHz, E-isomer): δ 0.88 (t, J = 7.0 Hz, 3H), 0.98 (d, J = 6.9 Hz, 3H), 1.19 (s, 6H), 1.21-1.39 (m, 18H), 1.40-1.50 (m, 2H), 1.57 (s, 3H), 1.87 (t, J = 7.4 Hz, 2H), 2.12 (septet, J = 6.9 Hz, 2H), 4.90 (d, J = 10.3 Hz, 1H), 4.95 (d, J = 17.1 Hz, 1H), 5.69 (m, 1H), 5.96 (s, 1H).

[0269] Example 16. 1-(((Z)-hex-3-en-1-yl)oxy)-2-methylundec-1-ene:

[0270] 2-Methylundecane (20 g, 87 mmol), cis-3-hexen-1-ol (26.1 g, 260 mmol) and dimethylacetal of KHSO4 (0.118 g, 0.87 mmol) were added to a 100 ml round bottom flask equipped with a Vigreux column (12 cm), a distillation head and a nitrogen bubbler. The mixture was heated at 150° C. for 1 hour while free methanol was distilled off. The Vigreux column was removed and heating was continued at 190° C. for 1 hour while free cis-3-hexen-1-ol was distilled off from the reaction flask. The mixture was cooled, placed under vacuum (5 Torr), and heated at 130° C. for 3 hours to remove residual hexenol. The enol ether was then separated from the reaction flask by vacuum distillation (bp 120-130°C, 25mTorr), followed by Kugelrohr distillation (115°C, 25mTorr) to afford the title compound (17.0 g, 63.8 mmol) as a colorless liquid in 73% yield (E / Z=56:44).

[0271] 1 H NMR (CDCl3, 600 MHz, E-isomer): δ 0.88 (t, J = 7.0 Hz, 3H), 0.96 (t, J = 7.5 Hz, 3H), 1.20-1.40 (m, 14H), 1.58 (s, 3H), 1.85 (t, J = 7.5 Hz, 2H), 2.03-2.09 (m, 2H), 2.31-2.38 (m, 2H), 3.65 (t, J = 7.0 Hz, 2H), 5.30-5.37 (m, 1H), 5.44-5.51 (m, 1H), 5.81 (s, 1H).

[0272] Examples 17 to 19.

[0273] Dimethyl acetal (35-60 mmol), alcohol (2 eq. mmol) and KHSO4 (48 mg, 0.35 mmol) were added to a 25-50 ml round bottom flask equipped with a distillation head and a nitrogen bubbler. The mixture was heated (oil bath at 150°C) while distilling off the released methanol (vapor temperature 64°C) until the vapor temperature dropped (40-60 minutes), indicating that most of the methanol had been removed. The mixture was placed under vacuum (300-500 mTorr) and heated (180-190°C oil bath) for 2-3 hours while distilling off the released alcohol from the reaction flask. After the addition of Na2CO3 (0.25-0.5 g), the enol ether was isolated from the reaction flask by vacuum distillation or by silica gel flash chromatography followed by Kugelrohr distillation.

[0274] Example 17. (2-((2-methyldec-1-en-1-yl)oxy)ethyl)benzene:

[0275] Starting from the dimethyl acetal of 2-methyldecanal and 2-phenylethanol, the title compound was isolated by distillation (bp 140-145°C, 20 mTorr) as a light yellow oil in 86% yield (E / Z=60:40).

[0276] 1 H NMR (CDCl3, 500 MHz, E-isomer): δ 0.88 (t, J = 6.9 Hz, 3H), 1.19-1.39 (m, 12H), 1.57 (s, 3H), 1.85 (t, J = 7.4 Hz, 2H), 2.92 (t, J = 7.3 Hz, 2H), 3.87 (t, J = 7.3 Hz, 2H), 5.82 (s, 1H), 7.17-7.30 (m, 5H).

[0277] Example 18. 1-((3,7-dimethyloct-6-en-1-yl)oxy)-2-methylundec-1-ene:

[0278] Starting from 2-methylundecanal and dimethyl acetal of citronellol, the title compound was isolated by distillation (bp 160°C, 50 mTorr) as a light yellow oil in 83% yield (E / Z = 58:42).

[0279] 1H NMR (CDCl3, 500 MHz, E-isomer): δ 0.88 (t, J = 7.1 Hz, 3H), 0.90 (d, J = 6.7 Hz, 3H), 1.22-1.45 (m, 17H), 1.56 (s, 3H), 1.60 (s, 3H), 1.68 (s, 3H), 1.55-1.73 (m, 2H), 1.85 (t, J = 7.5 Hz, 2H), 1.90-2.03 (m, 2H), 3.62-3.73 (m, 2H), 5.09 (t, J = 7.3 Hz, 2H), 5.80 (s, 1H).

[0280] Example 19. (2-((2-ethylhex-1-en-1-yl)oxy)ethyl)benzene:

[0281] Starting from the dimethyl acetal of 2-ethylhexanal and 2-phenylethanol, the title compound was isolated by distillation (bp 140-145°C, 500 mTorr) as a light yellow oil in a yield of 77% (isomer ratio = 57:43).

[0282] 1 H NMR (CDCl3, 500 MHz, isomer mixture): δ 0.89 (t, J = 7.0 Hz, 3H), 0.94, 0.96 (triplet, J = 7.6 Hz, 3H), 1.23-1.36 (m, 4H), 1.88, 1.89 (quartet, J = 7.6 Hz, 2H), 2.05, 2.07 (triplet, J = 7.4 Hz, 2H), 2.90 (t, J = 7.1 Hz, 2H), 3.84, 3.85 (triplet, J = 7.1 Hz, 2H), 5.77, 5.80 主要异构体 (single peak, 1H), 7.17-7.31 (m, 5H).

[0283] Examples 20 to 29.

[0284] Methoxymethyltriphenylphosphonium chloride (15.1 g, 44.1 mmol) and ketone (29.4 mmol) were added to 120 ml of toluene. Potassium tert-butoxide (5.27 g, 47 mmol) was added to the stirred slurry 4 times at 15-minute intervals. The mixture was stirred for 4 hours and turned dark red. It was then poured into 500 ml of water and extracted with EtOAc (3×250 mL). The organic phases were combined, dried over Na2SO4, filtered and concentrated. The resulting methyl enol ether product was separated by flash chromatography (silica gel, hexane) and then Kugelrohr distilled. The methyl enol ether (30-60 mmol) was then combined with 2-phenylethanol (2 equivalents) and KHSO4 (1 mol%) in a round-bottom flask (50 mL) equipped with a distillation head and a nitrogen bubbler. The mixture was heated (150°C oil bath) while distilling off the liberated methanol (vapor temperature 64°C) until the vapor temperature dropped (typically 40 minutes). The mixture was then placed under vacuum (300 mTorr) and heated at 180°C while allowing excess 2-phenylethanol to distill off the flask (typically 2 hours). After addition of Na2CO3 (0.25 g), the resulting enol ether was isolated from the reaction flask by vacuum distillation or by flash chromatography on silica gel. Product yields are reported for the conversion of the intermediate methyl enol ether to the isolated product.

[0285] Example 20. (Phenylethoxymethylene)cyclopentadecane:

[0286] The title compound was prepared starting from cyclopentadecanone. It was isolated as a colorless oil from the crude reaction mixture by short path distillation (bp>170°C, 25 mTorr) in 45% yield from the intermediate methyl enol ether.

[0287] 1 H NMR (CDCl3, 500MHz): δ1.16-1.52 (m, 24H), 1.87 (t, J = 7.1Hz, 2H), 2.03 (d, J = 7.4Hz ,2H),2.90(t,J=7.1Hz,2H),3.85(t,J=7.1Hz,2H),5.82(s,1H),7.17-7.31(m,5H).

[0288] Example 21. (2-((4-(tert-pentyl)cyclohexylene)methoxy)ethyl)benzene:

[0289] The title compound was prepared starting from 4-(tert-amyl)cyclohexan-1-one. It was isolated as a colorless oil by flash chromatography on silica gel (hexanes / EtOAc, 100:0->95:5) in 24% yield from the intermediate methyl enol ether.

[0290] 1H NMR (CDCl3, 500MHz): δ0.78 (s, 6H), 0.79 (t, J = 7.5Hz, 3H), 0.96 (qt, J = 12.7, 3.9H z,2H),1.20(tt,J=12.0,2.8Hz,1H),1.25(q,J=7.5Hz,2H),1.57(t,J=13.4Hz,1H) ,1.75(m,2H),1.85(t,J=13.4Hz,1H),2.08(d,J=13.4Hz,1H),2.82(d,J=13.5Hz, 1H), 2.91 (t, J = 7.2Hz, 2H), 3.86 (t, J = 7.2Hz, 2H), 5.78 (s, 1H), 7.17-7.31 (m, 5H).

[0291] Example 22. 9-(Phenylethoxymethylene)cyclododec-1,5-diene:

[0292] The title compound was prepared starting from cyclododeca-4,8-dien-1-one (mixture of E,E-, E,Z- and Z / E-isomers). The product was isolated as a colorless oil from the intermediate reaction mixture by short path distillation (bp 172°C, 30 mTorr) in 83% yield from the intermediate methyl enol ether (mixture of stereoisomers).

[0293] 1 H NMR (CDCl3, 500 MHz, isomer mixture): δ 1.30-1.61 (m, 2H), 1.80-2.23 (m, 12H), 2.87-2.96 (overlapping triplet, 2H), 3.82-3.94 (overlapping triplet, 2H), 5.06-5.57 (m 4H), 5.75, 5.77, 5.81, 5.84, 5.89 (singlet, 1H), 7.16-7.32 (m, 5H).

[0294] Example 23. (1SR, 4RS, 4aSR, 8aRS)-6-methyl-7-(phenethoxymethylene)decahydro-1,4-methylnaphthalene:

[0295] The title compound was prepared starting from (1RS,4SR,4aRS,8aSR)-7-methyloctahydro-1,4-naphthalen-6(2H)-one. The compound was isolated from the crude reaction mixture by short path distillation (bp 165-170°C, 15 mTorr) followed by Kugelrohr distillation (oven 150°C, 25 mTorr) as a pale yellow oil in 58% yield (mixture of four stereoisomers).

[0296] 1H NMR (CDCl3, 500 MHz, isomer mixture): δ 0.97, 0.98, 1.03, 1.07 (doublet, J = 6.9, 6.7, 7.2, 7.1 Hz, 3H), 1.00 (m, 2H), 1.10-1.24 (m, 2H), 1.28-1.60 (m, 7H), 1.61-1.76, 1.77-1.92 (m, 3H), 2.13, 2.41, 2.54, 2.67 (m, 1H), 2.91 (t, J = 7.2 Hz, 2H), 3.80-3.90 (overlapping triplet, 2H), 5.79, 5.84, 5.87 (singlet, 1H), 7.17-7.30 (m, 5H).

[0297] Example 24. (2-(((2RS,5SR)-2-isopropyl-5-methylcyclohexylidene)methoxy)ethyl)benzene:

[0298] The title compound was prepared starting from 2-isopropyl-5-methylcyclohexan-1-one (80% trans isomer). The compound was isolated from the crude reaction mixture by short path distillation (bp 130-135° C., 15 mTorr) as a pale yellow oil in 72% yield from the intermediate methyl enol ether (E / Z=60:40).

[0299] 1 H NMR (CDCl3, 500 MHz, isomer mixture): δ 0.77, 0.89 (triplet, J = 6.7, 7.0 Hz, 3H), 0.87, 0.90 (triplet, J = 6.7, 6.7 Hz, 6H), 0.93, 1.09, 1.18, 1.28 (m, 2H), [1.45-1.97 (m), 2.22 (dd, J = 1 3.5,5.3Hz),2.28(dt,J=10.4,3.8Hz),2.42(dd,J=12.8,3.8Hz)(7H)],2.85-2.94 (m,2H),3.78-3.92(m,2H),[5.78(d,J=1.4Hz),5.80(s)(1H)],7.18-7.33(m,5H).

[0300] Example 25. (2-((2-(2-((R)-4-methylcyclohex-3-en-1-yl)propyl)cyclopentylidene)methoxy)ethyl)benzene:

[0301] The title compound was prepared starting from 2-(2-((R)-4-methylcyclohex-3-en-1-yl)propyl)cyclopentan-1-one (4 diastereoisomers). The compound was isolated from the crude reaction mixture by Kugelrohr distillation (oven 220-225°C, 20 mTorr) as a colorless oil in 70% yield from the intermediate methyl enol ether (mixture of stereoisomers).

[0302] 1 H NMR (CDCl3, 500 MHz, isomer mixture): δ 0.80-0.88 (overlapping doublets, 3H), 0.91-2.46 (m, 17H), 1.64 (s, 3H), 2.90, 2.91 (overlapping triplets, J = 7.2 Hz, 2H), 3.82-3.92 and 3.89 (m and t, J = 7.2 Hz, 2H), 5.38 (br s, 1H), 5.83-5.87, 5.91-5.94 (br overlapping singlets, 1H), 7.17-7.30 (m, 5H).

[0303] Example 26. (2-((2-pentylcyclopentylidene)methoxy)ethyl)benzene:

[0304] The title compound was prepared starting from 2-pentylcyclopentan-1-one. The compound was isolated from the crude reaction mixture by Kugelrohr distillation (oven 160-180°C, 20 mTorr) as a colorless oil in 88% yield from the intermediate methyl enol ether (E / Z=62:38).

[0305] 1 H NMR (CDCl3, 500 MHz, E-isomer): δ 0.89 (t, J = 6.9 Hz, 3H), 1.09-1.39 (m, 8H), 1.39-1.56 (m, 2H), 1.60-1.75 (m, 2H), 1.75-1.86 (m, 1H), 2.07-2.17 (m, 1H), 2.28-2.36 (m, 1H), 2.91 (t, J = 7.2 Hz, 2H), 3.89 (t, J = 7.2 Hz, 2H), 5.87 (q, J = 2.2 Hz, 1H), 7.16-7.33 (m, 5H).

[0306] Example 27. (2-(((2-heptylcyclopentylidene)methoxy)ethyl)benzene:

[0307] The title compound was prepared starting from 2-heptylcyclopentan-1-one. The compound was isolated from the crude reaction mixture by Kugelrohr distillation (oven 195-205°C, 20 mTorr) as a colorless oil in 87% yield from the intermediate methyl enol ether (E / Z=62:38).

[0308] 1 H NMR (CDCl3, 500 MHz, E-isomer): δ 0.88 (t, J = 6.9 Hz, 3H), 1.10-1.38 (m, 12H), 1.38-1.55 (m, 2H), 1.60-1.74 (m, 2H), 1.74-1.86 (m, 1H), 2.08-2.18 (m, 1H), 2.28-2.37 (m, 1H), 2.92 (t, J = 7.2 Hz, 2H), 3.89 (t, J = 7.2 Hz, 2H), 5.87 (q, J = 2.1 Hz, 1H), 7.16-7.33 (m, 5H).

[0309] Example 28. (2-((2-ethyl-4,4-dimethylcyclohexylene)methoxy)ethyl)benzene:

[0310] The title compound was prepared starting from 2-ethyl-4,4-dimethylcyclohexan-1-one. The compound was isolated from the crude reaction mixture by Kugelrohr distillation (oven 140-145°C, 20 mTorr) as a pale yellow oil in 89% yield from the intermediate methyl enol ether (E / Z=91:9).

[0311] 1 H NMR (CDCl3, 500 MHz, E-isomer): δ 0.82 (t, J = 12.1 Hz, 1H), 0.89 (s, 3H), 0.90 (t, J = 7.4 Hz, 3H), 0.95 (s, 3H), 1.09-1.20 (m, 2H), 1.34-1.43 (m, 1H), 1.49-1.59 (m, 2H), 1.74 (td, J = 13.5, 4.4 Hz, 1H), 1.89 (sextet, J = 5.6 Hz, 1H), 2.66 (dt, J = 13.8, 3.9 Hz, 1H), 2.91 (t, J = 7.1 Hz, 2H), 3.87 (t, J = 7.1 H, 2H), 5.70 (s, 1H), 7.16-7.30 (m, 5H).

[0312] Example 29. (2-((2-ethyl-4-methylhex-1-en-1-yl)oxy)ethyl)benzene:

[0313] The title compound was prepared starting from 5-methylheptan-3-one. The compound was isolated from the crude reaction mixture by short path distillation as a pale yellow oil in a yield of 66% (isomer ratio = 58:42) from the intermediate methyl enol ether.

[0314] 1 H NMR (CDCl3, 500 MHz, isomer mixture): δ 0.80 (d, J = 6.7 Hz, 3H), 0.86, 0.87 (triplet, J = 7.4 Hz, 3H), 0.94, 0.95 (triplet, J = 7.8 Hz, 3H), 1.01-1.04 (m, 1H), 1.28-1.52 (m, 2H), 1.55-1.61, 1.84-2.14 (multiplet, 4H), 2.89, 2.90 (triplet, J = 7.0 Hz, 2H), 3.83, 3.86 (triplet, J = 7.0 Hz, 2H), 5.74, 5.86 主要异构体 (single peak, 1H), 7.17-7.31 (m, 5H).

[0315] 2. Headspace analysis in fabric softener applications

[0316] A model liquid fabric softener is prepared by mixing 12.3 wt % of TEA-esterquat (VL 90A), 0.4 wt % of a 10% calcium chloride aqueous solution, 0.04 wt % of Proxcel GXL, and 87.2 wt % of deionized water. Enol ether (0.075 mmol) is weighed into a vial and dissolved in 0.25 mL of acetone. Liquid fabric softener (4.5 g) is added to the vial and the mixture is shaken by hand to mix. Reference samples are prepared in the same manner using each 0.075 mmol of the released volatiles. The fabric softener sample is rinsed into a 3 L beaker with deionized water and the beaker is filled with a total volume of 1.5 L. Three 5 g cotton samples (approximately 12.5 × 12.5 cm, weight 270 g / m 2 , Item 403 from Testfabrics, West Pittston, PA) was added to the beaker and manually stirred for 3 minutes. After standing for another 2 minutes, the sample was removed and the excess water was squeezed out by hand. The cloth was hung to dry overnight (15-16 hours) at room temperature. The sample was then subjected to dynamic headspace analysis.

[0317] Each sample was placed in a headspace sampling cell (about 160 mL volume) at a constant temperature (25°C). Using an air sampling pump, a constant air flow (200 mL / min) was passed through the sampling cell and then through a 100 mg headspace sampler. Before entering the sample cell, the air was drawn through an activated carbon plug and then through a saturated NaCl solution to maintain a constant relative humidity of 75%. After 1 and 2 hours, the air was washed with clean The cartridge was replaced with the spent cartridge for 15 minutes to collect the headspace sample. The column was thermally desorbed using a Perkin Elmer TurboMatrix 650 thermal desorber (30 m, 0.25 mm ID, 0.25 μm membrane) connected to an Agilent 6890 gas chromatograph equipped with an Agilent 5975C mass spectrometer and a Varian VF-1 ms capillary column. The desorber parameters were: valve temperature 250°C, transfer line 250°C, purge time 1 minute, desorption temperature 240°C, desorption time 5 minutes, desorption flow 20 mL / min, trap at 40°C / sec from -30°C to 250°C, trap hold time 4 minutes, outlet split 48 mL / min, column flow rate 1 mL / min. The GC oven temperature profile was increased from 60°C (1 minute) to 210°C and then to 250°C (2 minutes) at a rate of 20°C / min. For the analysis of (Z)-3-hexen-1-ol (pipol), the initial oven temperature was 52 °C (2 min). The amount of each aroma volatile collected was determined using external calibration of various chemicals (reported as ng / L air). At least five acetone solutions were prepared with concentrations ranging from 0.05 g / L to 5 g / L of the analyte. The solutions were injected (0.2 μL) into the The solution was analyzed in triplicate. The calibration curve was forced through the origin.

[0318] Dynamic headspace concentrations (ng / L) of perfume raw materials prepared from line-dried cotton cloth treated with a fabric softener containing an enol ether fragrance precursor compared to the corresponding reference (data for 60-75 and 120-135 minute headspace samples, respectively).

[0319]

[0320]

[0321] a. The headspace injection pool is kept at a constant temperature of 30°C.

[0322] 3. Olfactory evaluation using leave-in hair conditioners

[0323] A model rinse-off hair conditioner was prepared in a generally known manner with the following composition (wt%):

[0324]

[0325] A 25% enol ether solution in isopropyl myristate or a 25% enol ether solution in acetone was dispersed in a leave-in hair conditioner to provide samples containing 0.15% or 0.25% by weight of the precursor, respectively. Reference samples of equimolar levels of the expected ketone and formates were prepared in the same manner. The samples were macerated at room temperature for one day. The hair samples (10 grams) were rinsed in warm tap water (37° C.) for 30 seconds and then gently combed to straighten the hair. The hair conditioner samples (1 g) were applied to the samples separately and then massaged into the hair to thoroughly disperse them. The samples were hung and dried at room temperature. After 6 hours and 24 hours, they were olfactorily evaluated by a panel for their odor intensity. Panelists were asked to rate the perceived odor intensity on a scale of 1 (barely noticeable) to 7 (very strong). The following table summarizes the data obtained from the panel evaluation.

[0326]

[0327] These data show that the compound of formula (I) produces a higher odor intensity on the hair compared to the corresponding reference sample at 6 hours and 24 hours after application from a leave-on hair conditioner. This shows that the compounds of the invention produce the desired sustained release effect.

[0328] 4. Olfactory Evaluation Using Rinse-Off Hair Conditioners

[0329] A model rinse-off hair conditioner was prepared in a generally known manner with the following composition (wt %).

[0330]

[0331] A 25% solution of the enol ether in isopropyl myristate was dispersed in a rinse-off hair conditioner to provide a conditioner containing 0.25 or 0.15% by weight of the precursor. Reference samples containing equimolar levels of the expected ketone and formates were prepared in the same manner. The samples were macerated at room temperature for one day. The hair samples (10 grams) were moistened with warm tap water (about 37° C.) and washed with an unperfumed milky shampoo. Shampoo (1 mL) was applied along the length of each hair sample using a syringe. The sample was massaged with fingertips for 30 seconds to disperse the shampoo and form a good foam. Rinse with warm tap water for 30 seconds, then gently squeeze out the excess water. Rinse the hair sample with a rinse-off hair conditioner (1.0 g) and gently massage it into the hair for 1 minute. The sample was then immersed in a 2-liter beaker with tap water, moved up and down 3 times, and then moved left and right 3 times. It was then rinsed with tap water for 30 seconds while detangling the hair with the fingertips. After gently squeezing out excess water, the samples were hung and dried at room temperature. After 6 hours and 24 hours, the samples were evaluated by a panel for odor intensity. The panelists were asked to rate the intensity of the perceived odor on a scale of 1 (barely perceptible) to 7 (very strong). The following table summarizes the data obtained from the panel evaluations.

[0332]

[0333] These data show that the compound of formula (I) produces a higher odor intensity on the hair compared to the corresponding reference sample at 6 hours and 24 hours after application from a rinse-off hair conditioner. This shows that the compounds of the invention produce the desired sustained release effect.

[0334] 5. Olfactory evaluation of pearlescent shampoo

[0335] A model pearlescent shampoo was prepared in a generally known manner with the following composition (wt%).

[0336]

[0337] A 25% enol ether solution in isopropyl myristate was dispersed in pearlescent shampoo to provide a sample containing 0.15% by weight of the precursor. Reference samples containing equimolar levels of the expected ketone and formate were prepared in the same manner. The samples were macerated at room temperature for one day. The hair samples (10 grams) were moistened with warm tap water (about 37°C) and then washed with a milky shampoo. Shampoo (1 gram) was applied with a syringe along the length of each hair sample. The sample was massaged with fingertips for 30 seconds to disperse the shampoo and form a good foam. Rinse with warm tap water for 30 seconds, and then the excess water was gently squeezed out. The sample was then washed again with pearlescent shampoo for 30 seconds and rinsed with warm tap water for 30 seconds. After gently squeezing out the excess water, the sample was hung and dried at room temperature. After 6 hours and 24 hours, a panel of 18 to 19 people came to smell and evaluate the odor intensity of the sample. Panelists were asked to score the perceived odor intensity on a scale of 1 (hardly perceptible) to 7 (very strong). The table below summarizes the data obtained from the group evaluation.

[0338]

[0339] These data show that the compound of formula (I) produces a higher odour intensity on the hair than the corresponding reference sample at 6 hours and 24 hours after application from the shampoo. This indicates that the compounds of the invention produce the desired sustained release effect.

[0340] 6. Olfactory evaluation using antiperspirant / deodorant sticks

[0341] A model deodorant was prepared in a generally known manner with the following composition (in % by weight).

[0342]

[0343] Samples containing 0.15 wt% of an enol ether fragrance precursor were prepared by dispersing a 15:20 mixture of an enol ether and isopropyl myristate in a molten antiperspirant composition. Reference samples containing equimolar levels of the expected ketone and formates were prepared in the same manner. The molten samples were poured into deodorant stick molds and allowed to macerate at room temperature for one day. 0.25 g of each sample was evenly dispersed on a 4.5 cm x 12 cm paper sniffing sheet. The sniffing sheets were stored at ambient conditions for 6 hours and 24 hours. After 6 hours and 24 hours, the odor intensity of the samples was olfactorily evaluated by a panel. Panelists were asked to rate the perceived odor intensity on a scale of 1 (barely noticeable) to 7 (very strong). The following table summarizes the data obtained from the panel evaluations.

[0344]

[0345] These data show that 6 hours after application of the antiperspirant stick, the compound of formula (I) produced a higher odor intensity on the scent paper than the corresponding reference sample. This indicates that the compounds of the present invention produce the desired sustained release effect.

[0346] 7. Olfactory evaluation in Eau de Toilette

[0347] A 1% solution of the enol ether in ethanol 40B and water (85:15 by weight) was prepared. A reference sample containing equimolar levels of the expected ketone and formate was prepared. If the mixture was not uniform, the enol ether and the corresponding reference sample were sonicated in a 25°C water bath for 10 to 20 minutes. 20 μl of each solution was applied to the center of a 4.5 cm×12 cm paper smelling sheet. The smelling sheet was stored under ambient conditions for 3 hours and 6 hours. After 6 hours and 24 hours, a panel of 20 to 25 people olfactorily evaluated the odor intensity of the samples. Panelists were asked to rate the perceived odor intensity on a scale of 1 (hardly perceptible) to 7 (very strong). The following table summarizes the data obtained from the panel evaluation.

[0348]

[0349] These data show that the compound of formula (I) produces a higher odor intensity on the scent paper than the corresponding reference sample 3 hours and 6 hours after application of the ethanol solution. This shows that the compound of the present invention produces the desired sustained release effect.

[0350] 8. Performance of the compounds of the present invention and the compounds disclosed in US 3004 / 0013779 (Comparative Example) in fabric softener applications

[0351] To compare the performance of these enol ethers as fragrance precursors, a fabric softener sample was prepared as described above by mixing 0.075 mmol of enol ether Example 1 with 0.075 mmol of any of the enol ether compounds disclosed in US 2004 / 0013779 (1-ethoxydodec-1-ene and 1-butoxydodec-1-ene) and 4.5 g of fabric softener. 1-Butoxydodec-1-ene was prepared according to Example 10 of US 2004 / 0013779 using dodecenal and 1-butanol as starting materials and separated into a mixture of isomers (E / Z=44:56). Cotton samples were rinsed with fabric softener samples, hung to dry (15-16 hours) and then subjected to dynamic headspace analysis as described above. The following table summarizes the average headspace concentrations of the released carbonyl compounds (2-undecanone or undecanal). In both cases, the headspace concentration of 2-undecanone released by Example 1 was significantly higher than the concentration of undecanal released by the comparative enol ethers 1-ethoxydodec-1-ene and 1-butoxydodec-1-ene. This indicates that the enol ethers of the present invention perform better as fragrance precursors than any of the enol ethers disclosed in US 2004 / 0013779. For the 60-75 minute headspace samples, the concentration of 2-undecanone released by Example 1 was up to 14 times and 3.3 times higher relative to the level of undecanal released by 1-ethoxydodec-1-ene or 1-butoxydodec-1-ene, respectively.

[0352] The following table summarizes the dynamic headspace concentrations (ng / L) of perfume raw materials made from line-dried cotton treated with fabric softeners of Example 1 and 1-ethoxydodec-1-ene or 1-butoxydodec-1-ene (data for 60-75 and 120-135 minute headspace samples and standard deviation).

[0353]

[0354] 9. Hydrolysis rate of the compound of the present invention and the compound disclosed in US 3004 / 0013779 A1 (Comparative Example)

[0355] Determination of the hydrolysis rates of Example 1, 1-ethoxydodec-1-ene and 1-butoxydodec-1-ene under acidic conditions ( Figure 1 ), as a predictor of stability in acidic consumer products. Susceptibility to acid-catalyzed hydrolysis will result in loss of the enol ether, thus limiting its long-term storage stability. Each enol ether was dissolved in a 4:1 THF / 0.1 M HCl mixture and the remaining percentage was measured over time relative to an internal standard as follows.

[0356] 125 mg of enol ether, 60 mg of hexadecane and 10 mL of THF (purged with N2 and containing 2500 ppm of BHT) were added to a 15 mL vial. After mixing, 2 mL of the solution was removed with a pipette and used to obtain a measurement at time zero. 2 mL of 0.1 M HCl was mixed with the remaining 8 mL of THF solution. The mixture was divided into 5 mL vials (1 mL per vial). The vials were gently covered with argon gas, fitted with screw caps, and wrapped with parafilm. The vials were stored at room temperature until analysis. For analysis, 2 mL of ethyl acetate was added to the vials and mixed. After phase separation, the top layer was collected and washed with saturated sodium carbonate (1 mL). Repeated samples of the organic phase were analyzed by GC-FID. For the zero time sample, 0.5 mL of deionized water was added to the 2 mL solution extracted from the original THF solution. 1 mL of the solution was added to a 5 mL vial, then diluted with 2 mL of ethyl acetate and mixed thoroughly. The top layer was collected. 1 mL of saturated sodium carbonate was added and mixed. Two samples of the top layer were then analyzed by GC-FID. The percentage of enol ether remaining was determined by comparing the ratio of the analyte to internal standard integrated peak areas to the ratio measured at time zero.

[0357] The following Figure 1 Both 1-ethoxydodec-1-ene and 1-butoxydodec-1-ene were shown to hydrolyze much more rapidly than Example 1. After six days, only 3% and 8.8% of 1-ethoxydodec-1-ene and 1-butoxydodec-1-ene, respectively, remained, whereas 83% of Example 1 remained intact. Thus, the enol ethers described in US 2004 / 00137791 were predicted to be unstable in acidic consumer products such as fabric softeners. This greater hydrolysis sensitivity and the resulting reduced stability are overcome due to the much slower hydrolysis rate of the enol ethers of the present invention.

[0358] 10. Preparation of liquid detergents containing the compounds of the present invention

[0359] Table 1: Composition of liquid detergent formulations

[0360]

[0361] 1) Hostapur SAS 60; Source: Clariant

[0362] 2) Edenor K 12-18; Source: Cognis

[0363] 3) Genapol LA 070; Source: Clariant

[0364] 4) Source: Genencor International

[0365] 5) Aculyn 88; Source: Dow Chemical

[0366] Liquid detergents were prepared by adding 0.005 to 5 wt % of one or more compounds of Examples 1 to 29, relative to the total weight of the liquid detergent, to the unperfumed liquid detergent formulation of Table 1 under gentle shaking.

[0367] 11. Preparation of a transparent homogeneous shampoo containing the compound of the present invention

[0368] Table 2: Composition of the transparent homogeneous shampoo formula

[0369]

[0370] 1) Ucare Polymer JR-400, source: Noveon

[0371] 2) Source: Schweizerhall

[0372] 3) Glydant, source: Lonza

[0373] 4) Texapon NSO IS, source: Cognis

[0374] 5) Tego Betain F 50, source: Evonik

[0375] 6)Amphotensid GB 2009, source: Zschimmer&Schwarz

[0376] 7) Monomuls 90L-12, source: Gruenau

[0377] 8) Monosodium paraben, Source: NIPA

[0378] The shampoo is prepared by dispersing Polyquaternium-10 in water. The remaining ingredients of Phase A are added one by one while mixing thoroughly after each adjuvant is added. This premix is ​​then added to the Polyquaternium-10 dispersion and mixed for an additional 5 minutes. Then, premixed Phase B and premixed Phase C (Monomuls 90L-12 is heated to melt in Texapon NSO IS) are added while stirring. Phase D and Phase E are added while stirring. The pH is adjusted with citric acid solution until pH: 5.5-6.0 to obtain an unperfumed shampoo formulation.

[0379] Perfumed shampoos are prepared by adding to the unperfumed shampoo formulation of Table 2 0.005 to 5 wt % of one or more compounds of Examples 1 to 29, relative to the total weight of the shampoo, under gentle shaking.

[0380] 12. Preparation of structured shower gel containing the composition of the present invention

[0381] Table 3: Composition of shower gel formula

[0382] Element Amount (% by weight) Deionized water 49.350 <![CDATA[Sodium EDTA 1) > 0.050 <![CDATA[Acrylic copolymer 2) > 6.000 <![CDATA[Sodium C12 - C15 alcohol polyether sulfate 3) > 35.000 Sodium hydroxide 20% aqueous solution 1.000 <![CDATA[Cocamidopropyl betaine 4) > 8.000 <![CDATA[Methylchloroisothiazolinone and methylisothiazolinone 5) > 0.100 Citric acid (40%) 0.500

[0383] 1) EDETA B powder; Trademark and source: BASF

[0384] 2) CARBOPOL AQUA SF-1 polymer; Trademark and source: NOVEON

[0385] 3) ZETESOL AO 328U; Trademark and source: ZSCHIMMER&SCHWARZ

[0386] 4)TEGO-BETAIN F 50; Trademark and source: GOLDSCHMIDT

[0387] 5) KATHON CG; Trademark and source: ROHM & HASS

[0388] Prepare a body wash by adding 0.005 to 5 wt % of one or more compounds of Examples 1 to 29, relative to the total weight of the body wash, to the unperfumed body wash formulation of Table 3 under gentle shaking.

[0389] 13. Preparation of a transparent shower gel comprising the composition of the present invention

[0390] Table 4: Composition of the transparent shower gel formula

[0391] Element Concentration (% by weight) Deionized water 52.40 <![CDATA[Sodium EDTA 1) > 0.10 Sodium Benzoate 0.50 Propylene glycol 2.00 <![CDATA[Sodium C12-C15 alcohol polyether sulfate 2) > 35.00 <![CDATA[Cocamidopropyl betaine 3) > 8.00 <![CDATA[Polyquaternium-7 4) > 0.20 Citric acid (40%) 1.00 Sodium chloride 0.80

[0392] 1) EDETA B powder; Trademark and source: BASF

[0393] 2) ZETESOL AO 328U; Trademark and source: ZSCHIMMER&SCHWARZ

[0394] 3)TEGO-BETAIN F 50; Trademark and source: GOLDSCHMIDT

[0395] 4) MERQUAT 550; Trademark and source: LUBRIZOL

[0396] A clear body wash was prepared by adding 0.005 to 5 wt % of one or more compounds of Examples 1 to 29, relative to the total weight of the body wash, to the unperfumed body wash formulation of Table 4 under gentle shaking.

[0397] 14. Preparation of a milky shower gel comprising the composition of the present invention

[0398] Table 5: Composition of the emulsion shower gel formula

[0399] Element Concentration (% by weight) Deionized water 50.950 <![CDATA[Sodium EDTA 1) > 0.050 Sodium Benzoate 0.500 Glycerin 86% 3.500 <![CDATA[Sodium dodecyl polyoxyethylene sulfate 2) > 27.000 <![CDATA[Polyquaternium-7 3) > 1.000 <![CDATA[Coco - Betaine 4) > 6.000 <![CDATA[PEG-120 Methyl Glucose Trioleate 5) > 1.000 Citric acid (40%) 1.000 <![CDATA[Ethylene glycol distearate & Laureth-4 & Cocamidopropyl betaine 6) > 3.000 Sodium chloride 20% 5.000 <![CDATA[PEG-40 Hydrogenated Castor Oil 7) > 1.000

[0400] 1) EDETA B powder; Trademark and source: BASF

[0401] 2)Texapon NSO IS; Trademark and source: COGNIS

[0402] 3) MERQUAT 550; Trademark and source: LUBRIZOL

[0403] 4)DEHYTON AB-30; Trademark and source: COGNIS

[0404] 5) GLUCAMATE LT; Trademark and source: LUBRIZOL

[0405] 6)EUPERLAN PK 3000AM; Trademark and source: COGNIS

[0406] 7) CREMOPHOR RH 40; Trademark and source: BASF

[0407] A clear body wash was prepared by adding 0.005 to 5 wt % of one or more compounds of Examples 1 to 29, relative to the total weight of the body wash, to the unperfumed body wash formulation of Table 5 under gentle shaking.

Claims

1. A method of releasing a compound selected from the group consisting of: a) Ketone of formula (II): Where R1 represents C 1-15 Alkyl, C 2-15 Alkenyl, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl or C 6-10 Aryl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, hydroxy and / or C 1-4 Carboxylate group; R2 represents C 1-15 alkyl; When R1 and R2 are combined together, C 5-15 Cycloalkyl, optionally substituted with one or more C 1-15 Alkyl, C 2-15 Alkenyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, 4-methylcyclohex-3-en-1-yl and / or C 1-4 Carboxylate group; R4 each independently represents hydrogen or C 1-5 alkyl; b) Formic acid esters of formula (III): Where R3 represents hydrogen, C 1-15 Alkyl, C 2-15 Alkenyl, C 3-15 Cycloalkyl or C 5-15 Cycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy and / or C 1-4 Carboxylate groups; R4 has the same meaning as defined above; and When R3 and R4 are combined together, C 3-15 Cycloalkyl, optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy and / or C 1-4 Carboxylate groups; c) Alcohols of formula (IV): wherein R3 and R4 have the same meanings as defined above; Wherein the precursor compound comprises a compound of formula (I): wherein R1, R2, R3 and R4 have the same meanings as defined above, or containing 9-(phenethoxymethylene)cyclododeca-1,5-diene; The method is carried out by exposing a precursor compound of formula (I) to an environment in which the compound is oxidized. Therein the precursor compound of formula (I) is oxidized under ambient conditions and in the absence of any catalyst.

2. The method according to claim 1, wherein R1 represents C 1-10 Alkyl, optionally substituted with C6 aryl, C 5-7 Cycloalkyl and / or C 5-7 Cycloalkenyl, each of which may be optionally substituted with one or more C 1-4 Alkyl and / or C 1-4 Alkoxy.

3. The method according to any one of claims 1 to 2, wherein R2 represents C 1-3 alkyl.

4. The method according to any one of claims 1 to 2, wherein R3 represents C 1-10 Alkyl, C 3-10 Alkenyl or C 5-15 Cycloalkyl, each of which is optionally substituted with one or more C 1-4 Alkyl, C6 aryl and / or C6 aryloxy.

5. A process according to any one of claims 1 to 2, wherein at least two of the compounds of formula (II), (III) or (IV) are perfuming ingredients.

6. The method according to any one of claims 1 to 2, wherein the environment in which the compound is oxidized is air.

7. Use of a compound of formula (I) according to any one of claims 1 to 6 as a perfuming ingredient for providing a long-lasting scent to an environment.

8. A method of imparting, enhancing, improving or modifying the odor characteristics of a perfuming composition, the air surrounding a perfuming composition, a surface or a perfumed article, comprising adding to said composition, said air or said article an effective amount of at least one compound of formula (I) as defined in any one of claims 1 to 6, or contacting or treating said surface with an effective amount of at least one compound of formula (I) as defined in any one of claims 1 to 6.

9. A method for intensifying or prolonging the diffusion of the characteristic aroma of at least one active ketone of formula (II), at least one active formate of formula (III) and / or at least one active alcohol of formula (IV) as defined in any one of claims 1 to 6 on a surface or in the air surrounding a perfuming composition, wherein the surface or the air is treated with at least one compound (I) as defined in any one of claims 1 to 6 or with a composition or preparation containing at least one compound (I) under conditions allowing the release of at least one active ketone of formula (II), at least one active formate of formula (III) and / or at least one active alcohol of formula (IV) 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 fragrance carrier and a fragrance base; and iii) optionally, at least one flavor 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 perfumed consumer product is a fabric care product, a body care product, a cosmetic preparation, or an air care product.

13. The perfumed consumer product according to claim 11, wherein the perfumed consumer product is a perfume, a skin care product or a home care product.

14. The perfumed consumer product according to claim 11, wherein the perfumed consumer product is a fine perfume, a wearable perfume or an eau de parfum, a cologne, a shaving lotion or aftershave, a fabric softener, a fabric refresher, an ironing water, paper, a bleaching agent, a carpet cleaner, a curtain care product, a shampoo, a coloring preparation, a color care product, a hair styling product, a dental care product, a disinfectant, a private care product, a hair spray, a deodorant or an antiperspirant, a depilatory, a tanning or sun protection product, a nail product, a skin cleanser, a foot / hand care product, an air freshener, a mildew remover, a wipe, a dishwashing detergent, a leather care product, or a car care product.

15. The perfumed consumer product according to claim 11, wherein the perfumed consumer product is a cosmetic, a "ready-to-use" powder air freshener or a hard surface detergent.

16. The perfumed consumer product according to claim 11, wherein the perfumed consumer product is a liquid or solid detergent.

17. The perfumed consumer product according to claim 11, wherein the perfumed consumer product is a hygiene product or a furniture care product.

18. The perfumed consumer product according to claim 11, wherein the perfumed consumer product is a vanishing cream, a soap, a bath mousse, a bath oil or a shower gel.

19. A compound of formula (I): Where R1 represents C 1-15 Alkyl, C 2-15 Alkenyl, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl or C 6-10 Aryl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy and / or C 1-4 Carboxylate group; R2 represents C 1-15 alkyl; When R1 and R2 are combined together, C 5-15 Cycloalkyl, optionally substituted with one or more C 1-15 Alkyl, C 2-15 Alkenyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy, 4-methylcyclohex-3-en-1-yl and / or C 1-4 Carboxylate group; R3 represents C 3-15 Alkenyl, C 3-15 Cycloalkyl or C 5-15 Cycloalkenyl, each of which is optionally substituted with one or more C 1-15 Alkyl, C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy and / or C 1-4 A carboxylate group, or C 1-15 Alkyl, optionally substituted with one or more C 1-15 Alkyl, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy and / or C 1-4 Carboxylate groups; R4 each independently represents hydrogen or C 1-5 alkyl; When R3 and R4 are combined together, C 3-15 Cycloalkyl, optionally substituted with one C 1-15 Alkyl and / or one or more C 1-15 Alkoxy, C 3-15 Cycloalkyl, C 5-15 Cycloalkenyl, C 6-10 Aryl and / or C 6-10 Aryloxy, each of which may be optionally substituted with one or more C 1-8 Alkyl, C 1-8 Alkoxy and / or C 1-4 a carboxylate group; and The compound of formula (I) is C 16 -C 28 Compounds, Alternatively, the compound of formula (I) is 9-(phenethoxymethylene)cyclododeca-1,5-diene; The conditions are: - When R1 is methyl, then R2 is not methyl or ethyl, - When R1 is ethyl, then R2 is not ethyl, - when R3 is an unsubstituted methyl group, then R4 is not a hydrogen atom or a methyl group, - when R3 is an unsubstituted ethyl group, then R4 is not a hydrogen atom, The condition is to exclude the following compounds: (((3,7-dimethyloct-1,6-dien-3-yl)oxy)methylene)cyclohexane, 3-(((2-ethylhex-1-en-1-yl)oxy)methyl]heptane, 4-(((7-methyloctyl)oxy)methylene)cyclohex-1-ene, 4-((Dodecyloxy)methylene)cyclohex-1-ene, (4-((4-phenylbutoxy)methylene)cyclohexyl)benzene, 1-((2-ethylhex-1-en-1-yl)oxy)octane, 1-((2-ethylhex-1-en-1-yl)oxy)dodecane, 2-Ethylhexenyl lauryl ether, 2-Ethylhexenyl octyl ether, 1-(2'-ethylhexyloxy)-2-ethyl-1,3-hexadiene, 1-((2-methylpent-1-en-1-yl)oxy)dodecane, 3-(Cyclohexylenemethoxy)-1,5,5-trimethylcyclohex-1-ene, (3-(Benzyloxy)-2-methylallyl)benzene, and 4-(4-(Allyloxy)-3-methylbut-3-en-1-yl)-1,2-dimethoxybenzene.

20. The compound according to claim 19, wherein R1 represents C 1-10 Alkyl, optionally substituted with C6 aryl, C 5-7 Cycloalkyl and / or C 5-7 Cycloalkenyl, each of which may be optionally substituted with one or more C 1-4 Alkyl and / or C 1-4 Alkoxy, R2 represents C 1-3 alkyl, R3 represents C 1-10 Alkyl, C 3-10 Alkenyl or C 5-15 Cycloalkyl, each of which is optionally substituted with one or more C 1-4 alkyl, C6 aryl and / or C6 aryloxy, and R4 each independently represents hydrogen or C 1-3 alkyl.

Images