Alkyl enol ether fragrance precursor

Abstract

To provide a perfuming composition and a fragrance-containing product for consumer which can maximize the impact of fragrance formulations by controlling the release profile of volatile fragrance compounds.SOLUTION: There is provided a compound of formula (I) as a perfuming component. In particular, there is provided a method for releasing a ketone of formula (II), a formate ester represented by formula: O=C-O-C(R3)(R4)2, and / or an alcohol represented by formula: HO-C(R3)(R4)2 by exposing the compound of formula (I) to an environment wherein it is oxidized. There is also provided a perfuming composition and a fragrance-containing consumer product which comprise at least one compound of formula (I).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to compounds of formula (I) as perfume precursor compounds. In particular, the present invention relates to a method for releasing a compound of formula (I) which is a ketone of formula (II), a formate of formula (III), and / or an alcohol of formula (IV) by placing the compound of formula (I) in an environment in which it is oxidized. Furthermore, the present invention relates to perfume compositions and consumer perfume products containing at least one compound of formula (I).

[0002] Background of the Invention The perfume industry is particularly interested in compositions or additives that can extend or enhance the fragrance effect of a mixture of multiple fragrances simultaneously over a certain period of time. Obtaining long-lasting properties is particularly desirable for standard fragrance ingredients that are too volatile, have poor substantivity themselves, or are deposited only in small amounts on end-use surfaces. Furthermore, some fragrance ingredients are unstable and need to be protected from gradual degradation before use. Long-lasting fragrances are desirable in various applications, such as high-quality or functional fragrances or cosmetics. Textile cleaning and softening is a particular area where there is a constant demand for active substances, particularly fragrances or fragrance compositions, that remain effective for a certain period of time after washing, softening, and drying. In fact, many active substances particularly suited to this type of application are known to lack adhesion to laundry or not remain on laundry during rinsing, resulting in their fragrance effect being short-lived and not very strong. Given the importance of this type of application in the perfume industry, research in this field has continued, particularly with the aim of finding new and more effective solutions to the aforementioned problems.

[0003] It has now surprisingly been found that the alkyl enol ether compounds according to the present invention solve the above-mentioned problems and are stable in consumer products while still being able to effectively release compounds which are ketones of formula (II), formates of formula (III), and / or alcohols of formula (IV). [Brief explanation of the drawings]

[0004] [Figure 1] FIG. 1 is an analysis of the concentrations of (2-((2-methylundec-1-en-1-yl)oxy)ethyl)benzene, 1-ethoxydodec-1-ene, and 1-butoxydodec-1-ene in acidic solution as a function of time.

[0005] Detailed Description Olfaction is a complex and dynamic process, and controlling the release behavior of volatile fragrance compounds can maximize the effectiveness of fragrance formulations and enrich the sensory experience. Perfume precursors, such as the compounds of the present invention, add a controlled and long-lasting dimension to the release behavior of highly volatile fragrance raw materials (PRMs).

[0006] Without intending to be limited to any particular theory, the compounds of the present invention may achieve their effect on the olfactory properties of a fragrance composition by tethering a PRM to a molecular anchor and requiring a specific reaction mechanism under specific environmental conditions to release the volatile PRM from this anchor. In the present invention, the release of one, two, or up to three PRMs is driven by oxidation of the perfume precursor when it is exposed to oxygen in the ambient air.

[0007] In a first aspect, the present invention provides a method for producing a compound of formula (I) from a precursor compound: a) a ketone of formula (II) [ka] [In the formula, R1 is C 1~8 Alkyl, C 1~8 Alkoxy, hydroxy, carboxylic acid, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~15 Alkyl, C 1~15 Alkoxy, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 6~10aryl, and / or C 6~10 C, each optionally substituted with one or more aryloxy groups 1~15 Alkyl, C 2~15 Alkenyl, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, or C 6~10 represents an aryl group; R2 is C 1~15 represents an alkyl group; R1 and R2, when taken together, are C 1~8 Alkyl, C 1~8 Alkoxy, carboxylic acid, 4-methylcyclohex-3-en-1-yl, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 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 C, each optionally substituted with one or more aryloxy groups 5~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 4~14 Heterocycloalkyl, or C 4~14 forming heterocycloalkenyl groups, the heteroatoms of which represent one or more oxygens; R4 is independently hydrogen or C 1~5 represents an alkyl group; R1 and R4, when taken together, are C 1~8 Alkyl, C 1~8 Alkoxy, carboxylic acid, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~15 Alkyl, C 1~15 Alkoxy, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 6~10 aryl, and / or C 6~10C, each optionally substituted with one or more aryloxy groups 3~15 Cycloalkyl or C 5~15 forming a cycloalkenyl group]; b) a formate ester of formula (III) [ka] [In the formula, R3 represents hydrogen or C 1~8 Alkyl, C 1~8 Alkoxy, carboxylic acid, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~15 Alkyl, C 1~15 Alkoxy, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 6~10 aryl, and / or C 6~10 C, each optionally substituted with one or more aryloxy groups 1~15 Alkyl, C 2~15 Alkenyl, C 3~15 Cycloalkyl, or C 5~15 represents a cycloalkenyl group; R4 has the same meaning as defined above; R3 and R4, when taken together, are C 1~8 Alkyl, C 1~8 Alkoxy, carboxylic acid, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~15 Alkyl, C 1~15 Alkoxy, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 6~10 aryl, and / or C 6~10 C, each optionally substituted with one or more aryloxy groups 3~15 Cycloalkyl or C 5~15 forming a cycloalkenyl group]; c) an alcohol of formula (IV) [ka] wherein R3 and R4 have the same meanings as defined above; 1. A method for releasing a compound selected from the group consisting of: at least one of the compounds of formula (II), (III), or (IV) is the active compound; The precursor compound is a compound of formula (I) [ka] [wherein R1, R2, R3, and R4 have the same meanings as defined above]; wherein said release occurs by placing the precursor compound of formula (I) in an environment where it is oxidized, i.e. ambient conditions.

[0008] "Active compound," "active volatile compound," "active volatile ketone, formate, and / or alcohol," or similar terms, are understood to refer to ketone, formate, and / or alcohol compounds capable of providing a benefit or effect to their surrounding environment. In particular, "active compounds" are selected from the group consisting of fragrance components, flavor components, malodor-neutralizing components, and insect repellent or attractant components. Thus, to be considered an "active compound," a compound must possess at least one property that makes it useful as a fragrance component, a malodor-neutralizing component, a flavor component, and / or an insect repellent or attractant.

[0009] The term "perfuming ingredient" is understood as a compound used as an active ingredient in a fragrance formulation or composition to impart a hedonic effect. In other words, a compound to be considered a perfuming ingredient must not only have an odor, but must also be recognized by those skilled in the perfumery arts as being able to impart or modify the odor of the composition in a positive or pleasant way. The term "flavor-imparting ingredient" is understood as being able to impart a taste sensation to the taster's palette. The term "malodor-neutralizing ingredient" is understood as being able to reduce the perception of malodor, i.e., an unpleasant or unpleasant odor to the human nose. The term "insect attractant or repellent" is understood as a compound that has a positive or negative effect on insects. Examples of insect attractants or repellents can be found in reference texts such as A.M. El-Sayed, The Pherobase 2005, http: / / www.pherobase.net, or other works of a similar nature.

[0010] According to the above and below embodiments of the present invention, the method of the present invention is particularly useful when the active compound is a perfuming ingredient, i.e., a perfuming ketone, formate ester, and / or alcohol. "Perfuming ketone, formate ester, and / or alcohol" refers to compounds used in the perfume industry, i.e., compounds used as active ingredients in perfume formulations or compositions to impart a hedonic effect. In other words, such ketones, formates, and / or alcohols not only have an odor, but should be recognized by those skilled in the perfume industry as being able to impart or modify the odor of a composition in a positive or pleasant way. Perfuming ketones, formates, and / or alcohols may be of natural or synthetic origin. Many of these co-components are described in reference texts, such as S. Arctander's book "Perfume and Flavor Chemicals," 1969 (Montclair, New Jersey, USA), or its later editions, or other works of a similar nature, as well as in the abundant patent literature in the field of perfumery.

[0011] The term "perfuming ketones, formates and / or alcohols" as used herein is also referred to as "perfuming compounds".

[0012] In fact, the invention operates in exactly the same way regardless of the exact nature of the active ketone, formate, or alcohol. Thus, even though the invention is described in detail hereinafter with specific reference to "perfuming compounds," it will be understood that the following embodiments are also applicable to other active ketones, formates, and / or alcohols (i.e., for example, "perfuming" can be replaced with "flavoring," "malodor-neutralizing," "insect-attracting," or "insect-repelling").

[0013] The term "optionally" is understood to mean that the particular optionally substituted group may or may not be substituted with the particular substituent, and the term "one or more" is understood to mean that the particular group is substituted with 1 to 7, preferably 1 to 5, and more preferably 1 to 3, of the particular functional groups.

[0014] 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 one, two, or three olefinic double bonds, preferably one or two 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 groups, preferably monocyclic cycloalkyl, cycloalkenyl, heterocycloalkyl, and heterocycloalkenyl groups.

[0015] The term "aryl" is understood to include any group that contains at least one aromatic group, such as a phenyl, indenyl, indanyl, tetrahydronaphthalenyl, or naphthalenyl group.

[0016] "C 1~15 The term "alkoxy" refers to any group where R is a straight, branched, cyclic, or aliphatic C 1~15 It is understood that the group RO- is an alkyl or alkenyl group.

[0017] According to any one of the above embodiments of the present invention, said compound (I) is 16~28 Compounds, especially C 18~26 Compounds, more specifically C 19~24 It is a compound.

[0018] In a preferred embodiment, when "R1 and R4 taken together" and / or "R3 and R4 taken together" form a cycloalkenyl group, it is understood that an olefinic double bond is not adjacent to the carbon connecting R1 and R4 or R3 and R4, respectively. In a preferred embodiment, when an alkenyl group is substituted with an alkoxy group, the alkoxy group cannot form an enol ether adjacent to the olefinic double bond of the alkenyl group.

[0019] According to an optional embodiment of the present invention, R1 is C 1~4 Alkyl, C 1~4 Alkoxy, carboxylic acid, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~4 Alkyl, C 1~4 Alkoxy, C 3~8 Cycloalkyl, C 5~8 C, each optionally substituted with one or more cycloalkenyl, C aryl, and / or C aryloxy groups. 1~10 Alkyl, C 2~10 Alkenyl, C 3~11 Cycloalkyl, or C 5~11 represents a cycloalkenyl group.

[0020] According to an optional embodiment, R1 is C 1~4 Alkyl or C 1~4 C, each optionally substituted with one or more alkoxy groups 1~4 Alkyl, C 1~4 Alkoxy, C 3~8 Cycloalkyl, C 5~8 C, each optionally substituted with one or more cycloalkenyl, C aryl, and / or C aryloxy groups. 1~10 Alkyl, C 2~10 Alkenyl, or C 3~11 represents a cycloalkyl group.

[0021] According to an optional embodiment, R1 is C 1~4 Alkyl and / or C 1~4 C, each optionally substituted with one or more alkoxy groups 5~7 Cycloalkyl, C 5~7 C, each optionally substituted with a cycloalkenyl, and / or C aryl group 1~10 Preferably, R1 is a C alkyl group, each of which may be optionally substituted with one or more methyl and / or methoxy groups. 5~7 Cycloalkyl, C 5~7 C optionally substituted with cycloalkenyl, and / or C aryl groups 1~10 represents an alkyl group.

[0022] According to an optional embodiment, R2 is C 1~10 In certain embodiments, R represents an alkyl group. 1~5 In certain embodiments, R represents an alkyl group. 1~3 It represents an alkyl group, preferably a methyl group or an ethyl group.

[0023] According to an optional embodiment, R1 and R2, when taken together, form C 1~5 Alkyl, C 1~5Alkoxy, carboxylic acid, 4-methylcyclohex-3-en-1-yl, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~7 Alkyl, C 2~8 Alkenyl, C 1~5 Alkoxy, C 3~8 Cycloalkyl, C 5~8 C, each optionally substituted with one or more cycloalkenyl or C aryl groups 5~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 4~15 Heterocycloalkyl, or C 4~15 It forms a heterocycloalkenyl group, where the heteroatom represents one or more oxygens.

[0024] According to certain embodiments, R1 and R2, when taken together, are 1 to 4 C 1~7 Alkyl or C 2~8 C, each optionally substituted with an alkenyl group 5~15 Cycloalkyl or C 5~15 Forms a cycloalkenyl group.

[0025] According to an optional embodiment, R1 and R2, when taken together, form C 1~5 Alkyl, C 1~5 Alkoxy, carboxylic acid, 4-methylcyclohex-3-en-1-yl, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~7 Alkyl, C 2~8 Alkenyl, C 1~5 Alkoxy, C 3~8 Cycloalkyl, C 5~8 C, each optionally substituted with one or more of a cycloalkenyl, or C aryl group 5~11 Cycloalkyl, C 5~11 Cycloalkenyl, C 4~11 Heterocycloalkyl, or C 4~11It forms a heterocycloalkenyl group, where the heteroatom represents one or more oxygens.

[0026] In certain embodiments, R1 and R2, when taken together, are C 1~5 Alkyl, C 1~5 Alkoxy, carboxylic acid, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~5 Alkyl, C 1~5 Alkoxy, C 3~8 Cycloalkyl, C 5~8 C, each optionally substituted with one or more of a cycloalkenyl, or C aryl group 5~11 Cycloalkyl, C 5~11 Cycloalkenyl, C 4~11 Heterocycloalkyl, or C 4~11 It forms a heterocycloalkenyl group, where the heteroatom represents one or more oxygens.

[0027] According to an optional embodiment, R1 and R2, when taken together, form C 1~3 Alkyl, C 1~3 Alkoxy, carboxylic acid, 4-methylcyclohex-3-en-1-yl, and / or C 1~3 C, each optionally substituted with one or more carboxylic acid ester groups 1~7 Alkyl, C 2~6 Alkenyl, C 1~4 Alkoxy, C 5~7 Cycloalkyl, C 5~7 C, each optionally substituted with one or more of a cycloalkenyl, or C aryl group 5~7 Cycloalkyl, C 5~7 Cycloalkenyl, C 5~7 Heterocycloalkyl, or C 5~8 They form heterocycloalkenyl groups, the heteroatoms of which represent one or more oxygens.

[0028] In certain embodiments, R1 and R2, when taken together, are C1~3 Alkyl, C 1~3 Alkoxy, carboxylic acid, and / or C 1~3 C, each optionally substituted with one or more carboxylic acid ester groups 1~4 Alkyl, C 1~4 Alkoxy, C 5~7 Cycloalkyl, C 5~7 C, each optionally substituted with one or more of a cycloalkenyl, or C aryl group 5~7 Cycloalkyl, C 5~7 Cycloalkenyl, C 5~7 Heterocycloalkyl, or C 5~8 It forms a heterocycloalkenyl group, where the heteroatom represents one or more oxygens.

[0029] According to an optional embodiment, R1 and R2, when taken together, form C 1~7 Alkyl, C 2~6 Alkenyl group, or C 1~4 C, each optionally substituted with one or more alkoxy groups 5~7 Cycloalkyl or C 5~7 Forms a cycloalkenyl group.

[0030] According to an optional embodiment, R1 and R2, when taken together, form C 1~4 Alkyl, C 2~6 Alkenyl, or C 1~4 C, each optionally substituted with one or more alkoxy groups 5~7 Cycloalkyl or C 5~7 Forms a cycloalkenyl group.

[0031] According to an optional embodiment, R1 and R2, when taken together, are each optionally substituted with one methyl group. 10~15 Cycloalkyl or C 10~15 R1 and R2, when taken together, form a cycloalkenyl group, or R1 and R2, when taken together, form a cycloalkenyl group, 1~7 Alkyl, C 2~6Alkenyl or C 1~4 C, each optionally substituted with an alkoxy group 5~6 Cycloalkyl or C 5~6 Forms a cycloalkenyl group.

[0032] According to an optional embodiment, each R4 is independently a hydrogen atom or C 1~5 In certain embodiments, each R4 independently represents a hydrogen atom or a C 1~3 In certain embodiments, each R independently represents a hydrogen atom, and only one R is C 1~3 In certain embodiments, each R independently represents a hydrogen atom, and only one R is C 1~2 represents an alkyl group. In a preferred embodiment, each R4 represents a hydrogen atom.

[0033] According to an optional embodiment, R1 and R4 adjacent to R1, when taken together, are C 1~4 Alkyl or C 1~4 C, each optionally substituted with one or more alkoxy groups 1~5 Alkyl, C 1~5 Alkoxy, C 3~7 Cycloalkyl, C 5~7 C, each optionally substituted with one or more cycloalkenyl, and / or C aryl groups 3~11 Cycloalkyl or C 5~11 Forms a cycloalkenyl group.

[0034] According to an optional embodiment, R1 and R4, when taken together, form C 1~3 Alkyl or C 1~3 C, each optionally substituted with one or more alkoxy groups 3~11 Cycloalkyl or C 5~11 Forms a cycloalkenyl group.

[0035] According to an optional embodiment, R1 and R4, when taken together, form C1~3 Alkyl or C 1~3 C, each optionally substituted with one or more alkoxy groups 3~11 Forms a cycloalkyl group.

[0036] According to an optional embodiment, R3 is C 1~5 Alkyl or C 1~5 C, each optionally substituted with one or more alkoxy groups 1~5 Alkyl, C 1~5 Alkoxy, C 3~8 Cycloalkyl, C 5~8 C, each optionally substituted with one or more cycloalkenyl, C aryl, and / or C aryloxy groups. 1~10 Alkyl, C 2~10 Alkenyl, C 3~15 Cycloalkyl, or C 5~11 represents a cycloalkenyl group.

[0037] According to an optional embodiment, R3 is C 1~3 Alkyl or C 1~3 C, each optionally substituted with one or more alkoxy groups 1~4 Alkyl, C 1~4 Alkoxy, C 5~6 Cycloalkyl, C 5~6 C, each optionally substituted with one or more cycloalkenyl, C aryl, and / or C aryloxy groups. 1~10 Alkyl, C 3~10 Alkenyl, C 4~15 Cycloalkyl, or C 5~11 represents a cycloalkenyl group.

[0038] According to an optional embodiment, R3 is C 1~4 C, each optionally substituted with one or more alkyl, C aryl, and / or C aryloxy groups 1~10 Alkyl, C 3~10 Alkenyl, or C 5~15 represents a cycloalkyl group.

[0039] According to an optional embodiment, R3 represents a benzyl, phenoxymethyl, heptyl, pentyl, 4-methylhex-5-en-1-yl or pent-5-en-1-yl group.

[0040] According to an optional embodiment, R3 and R4 adjacent to R3, when taken together, are C 1~4 Alkyl or C 1~4 C, each optionally substituted with one or more alkoxy groups 1~5 Alkyl, C 1~5 Alkoxy, C 3~7 Cycloalkyl, C 5~7 C, each optionally substituted with one or more cycloalkenyl, and / or C aryl groups 3~12 Cycloalkyl or C 5~11 Forms a cycloalkenyl group.

[0041] According to an optional embodiment, R3 and R4, when taken together, form C 1~3 Alkyl or C 1~3 C, each optionally substituted with one or more alkoxy groups 3~12 Cycloalkyl or C 5~11 Forms a cycloalkenyl group.

[0042] According to an optional embodiment, R3 and R4, when taken together, form C 1~3 Alkyl or C 1~3 C, each optionally substituted with one or more alkoxy groups 3~12 Forms a cycloalkyl group.

[0043] In certain embodiments, the ketone of formula (II), the formate of formula (III), and / or the activated alcohol of formula (IV) are perfuming ingredients. It will also be apparent to those skilled in the art that the compounds according to the present invention are essentially volatile compounds.

[0044] The ketone, formate, and / or alcohol may be advantageously characterized by a vapor pressure greater than 1.0 Pa, as 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, formate, and / or alcohol may be greater than 5.0 Pa, or even greater than 7.0 Pa.

[0045] In a preferred embodiment, the compound of formula (I) is non-volatile.The compound of formula (I) can be advantageously characterized by a vapor pressure of less than 0.01 Pa, which is calculated using software EPIwin v. 3.10 (2000, available from the United States Environmental Protection Agency).According to a preferred embodiment, this vapor pressure is less than 0.001 Pa.

[0046] In certain embodiments, the ketone of formula (II) is 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 (dihydrotagetone), 2-(sec-butyl)cyclohexane-1-one, 2-(tert-butyl)cyclohexane-1-one, 4 ... -(tert-Pentyl)cyclohexan-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-methanonaphthalen-6(2H)-one, thujopsan-4-one, 1,3,3-trimethylbicyclo[2.2.1]Heptanone-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)- (2,6,6-trimethylcyclohex-1-en-1-yl)butan-2-one (dihydro-alpha-ionone), 4-(2,6,6-trimethylcyclohex-1-en-1-yl)butan-2-one (dihydro-beta-ionone), (5-E / Z)-6,10-dimethylundeca-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-methanonaphthalen-5(1H)-one, 2-pentylcyclo Pentan-1-one, 2-heptylcyclopentan-1-one, 2-(hex-5-en-1-yl)cyclopentan-1-one, 2,2,5-trimethyl-5-pentylcyclopentan-1-one, methyl 2-(3-oxo-2-pentylcyclopentyl)acetate, Iso-E-Super, methyl jasmonate, 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, iso-longifolanon, 1-(3,3-dimethylcyclohexyl)ethan-1-one, 2,6,6-trimethylcycloheptan-1-one, 3,6,8,8-tetramethylhexahydro-1H-3a,7-methanoazulen-5(4H)-one, and 2-(2-(4-methylcyclohex-3-en-1-yl)propyl)cyclopentan-1-one.

[0047] In more specific embodiments, the ketone of formula (II) is 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-methanonaphthalen-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-methyl ... -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-alpha-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.

[0048] In certain embodiments, the formate 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, butan-2-yl formate, 2-methylpropyl formate, cyclohexyl formate, hexyl formate, heptyl formate, octyl formate, nonyl formate, decyl formate, 3-octyl formate, benzyl formate, 3,7-dimethyloct-6-enyl formate, and methyl formate. 3,7-Dimethyloct-7-enyl formate, Cinnamyl formate, 4-Methoxybenzyl formate, (E)-3,7-dimethylocta-2,6-dien-1-yl formate, (Z)-3,7-dimethylocta-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, 3-Methylbut-2-enyl formate Formate, Bornyl Formate, Isobornyl Formate, 2-Methyl-5-(prop-1-en-2-yl)cyclohex-2-en-1-yl Formate, Cedryl Formate, Cyclododecyl Formate, Decahydronaphthalen-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 Formate, Formic Acid 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-dimethylocta-1,6-dien-3-yl formate, 2,6-dimethyloct-7-en-2-ol formate, 1-((2-(tert-butyl)cyclohexyl)oxy)butan-2-yl formate.

[0049] In more specific embodiments, the formate ester of formula (III) is 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)hexan-3-yl formate, hexyl formate, benzyl formate, octan-3-yl formate, (1RS,2SR, 5RS)-2-isopropyl-5-methylcyclohexyl formate, cyclododecayl 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-dimethyloctan-3-yl formate, 2-methyl-1-phenylpropan-2-yl formate, and 2,6-dimethylheptan-2-yl formate.

[0050] In certain embodiments, the alcohol of formula (IV) is 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, methyl ... Alcohol, 4-methoxybenzyl alcohol, (E)-3,7-dimethylocta-2,6-dien-1-ol, (Z)-3,7-dimethylocta-2,6-dien-1-ol, 2-hexen-1-ol, 3-hexen-1-ol, 3,5,5-trimethylhexanol, 2-phenylethanol, 2-(phenoxy)ethanol, 3-phenylpropanol, 2-phenylpropan-1-ol, 1-phenylethan-1-ol, 4-phenylbutan-2-ol, 3-methylbut-2-en-1-ol, (Z)-6-nonen- 1-ol, borneol, isoborneol, 2-methyl-5-(prop-1-en-2-yl)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-dimethylocta-1,6-dien-3-ol, 2,6-dimethyloct-7-en-2-ol, 2,6-dimethyloctan-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, and 2-methyl-1-phenylpropan-2-ol.

[0051] 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.

[0052] According to an optional embodiment, the compound of formula (I) is (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)undec-1-ene, (3-methyl-4-(octyloxy)but-3-en-1-yl)benzene, 1-methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene, 2-methyl-1-(octan-3-yloxy)undec-1-ene, (3-methyl-4-(octan-3-yloxy)but-3-en-1-yl)benzene, 1-methoxy-4-(2-methyl-3-(octan-3-yloxy) (2-methylundec-1-en-1-yl)oxy) cyclododecane, 1-((2,6-dimethyloct-7-en-2-yl)oxy)-2-methylundec-1-ene, 1-(((Z)-hex-3-en-1-yl)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,4aSR,8aRS)-6-methyl-7-(phenethoxymethylene)decahydro-1,4-methanonaphthalene, (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 the group consisting of (2-((2-methylundec-1-en-1-yl)oxy)ethyl)benzene and 1-methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene.

[0053] In certain embodiments, at least two of the compounds of formula (II), (III), and (IV) are active compounds.

[0054] In more specific embodiments, compounds of formula (II), (III), and (IV) are the active compounds.

[0055] According to an optional 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 oxidizing the precursor compound of formula (I) under ambient conditions. Furthermore, the precursor compound of formula (I) is oxidized under ambient conditions and in the absence of a catalyst. For clarity, "ambient conditions" or similar expressions are intended to have the ordinary meaning understood by those skilled in the art, i.e., oxidation occurs at room temperature, in air, and at atmospheric pressure. In other words, the environment in which the compound is oxidized is air. It is understood hereby that the compound of formula (I) is oxidized in ambient air. In particular, it is understood that the compound of formula (I) does not require a pure oxygen environment, heat, or a catalyst to be oxidized.

[0056] Without intending to be limited to 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 evaporation rate of the ketone of formula (II), the formate of formula (III), or the alcohol of formula (IV), respectively.

[0057] In some embodiments, the rate at which the precursor compound of formula (I) is oxidized, and thereby the rate at which each of the ketone of formula (II), the formate of formula (III), or the alcohol of formula (IV) is released, enhances or prolongs the characteristic aroma diffusion effect and / or perception of the at least one active ketone of formula (II), the at least one active formate of formula (III), and / or the at least one active alcohol of formula (IV) as defined above.

[0058] In one embodiment, 100% of the compounds of Formula (I) are oxidized in ambient air in a period ranging from 24 hours to 48 hours. Alternatively, 90% of the compounds of Formula (I) are oxidized in ambient air in a period ranging from 24 hours to 48 hours. Alternatively, 80% of the compounds of Formula (I) are oxidized in ambient air in a period ranging from 24 hours to 48 hours. Alternatively, 70% of the compounds of Formula (I) are oxidized in ambient air in a period ranging from 24 hours to 48 hours. Alternatively, 60% of the compounds of Formula (I) are oxidized in ambient air in a period ranging from 24 hours to 48 hours. Alternatively, 50% of the compounds of Formula (I) are oxidized in ambient air in a period ranging from 24 hours to 48 hours. Alternatively, 40% of the compounds of Formula (I) are oxidized in ambient air in a period ranging from 24 hours to 48 hours. Alternatively, 30% of the compounds of formula (I) are oxidized in ambient air over a period ranging from 24 hours to 48 hours. Alternatively, 20% of the compounds of formula (I) are oxidized in ambient air over a period ranging from 24 hours to 48 hours. Alternatively, 10% of the compounds of formula (I) are oxidized in ambient air over a period ranging from 24 hours to 48 hours. Alternatively, 9% of the compounds of formula (I) are oxidized in ambient air over a period ranging from 24 hours to 48 hours. Alternatively, 8% of the compounds of formula (I) are oxidized in ambient air over a period ranging from 24 hours to 48 hours. Alternatively, 7% of the compounds of formula (I) are oxidized in ambient air over a period ranging from 24 hours to 48 hours. Alternatively, 6% of the compounds of formula (I) are oxidized in ambient air over a period ranging from 24 hours to 48 hours. Alternatively, 5% of the compounds of formula (I) are oxidized in ambient air over a period ranging from 24 hours to 48 hours. Alternatively, 4% of the compound of formula (I) is oxidized in ambient air for a period ranging from 24 hours to 48 hours. Alternatively, 3% of the compound of formula (I) is oxidized in ambient air for a period ranging from 24 hours to 48 hours. Alternatively, 2% of the compound of formula (I) is oxidized in ambient air for a period ranging from 24 hours to 48 hours. Alternatively, 1% of the compound of formula (I) is oxidized in ambient air for a period ranging from 24 hours to 48 hours.

[0059] In certain embodiments, the compound of formula (I) is encapsulated. At least one compound of formula (I) can be encapsulated in a microcapsule. In a preferred embodiment, at least one compound of formula (I) is encapsulated in a core-shell microcapsule, where 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 the environment. The shell is made of a material capable of releasing the compound of formula (I) and / or the active compounds of formula (II), (III), and / or (IV). In a preferred embodiment, the shell is made of a material capable of releasing the compound of formula (I) and / or the active compounds of formula (II), (III), and / or (IV) upon rupture of the shell and / or by diffusion through the shell. Those skilled in the art are well aware of methods for producing such microcapsules.

[0060] The nature of the polymer shell from the microcapsules of the present invention can vary. By way of non-limiting example, the shell can be based on aminoplast, polyurea, or polyurethane. The shell can also be hybrid, i.e., organic-inorganic, such as a hybrid shell composed of at least two types of inorganic particles crosslinked together, or a shell obtained by the hydrolysis and condensation reaction of a polyalkoxysilane macromonomer composition.

[0061] According to one embodiment, the shell comprises an aminoplast copolymer such as melamine-formaldehyde, or urea-formaldehyde, or crosslinked melamine formaldehyde, or melamine glioxal.

[0062] According to another embodiment, the shell is a polyurea-based material, for example, but not limited to, made from an isocyanate-based monomer and an amine-containing crosslinker, such as guanidine carbonate and / or guanazole. Preferred polyurea microcapsules comprise a polyurea wall that is the reaction product of polymerization between at least one polyisocyanate containing at least two isocyanate functional groups and at least one reactant selected from the group consisting of amines (e.g., water-soluble guanidine salts and guanidine); a colloidal stabilizer or emulsifier; and an encapsulated fragrance. However, the use of the amine can be omitted.

[0063] According to a particular embodiment, the colloidal stabilizer comprises an aqueous solution of 0.1% to 0.4% polyvinyl alcohol and 0.6% to 1% cationic copolymer of vinylpyrrolidone and quaternized vinylimidazole (all percentages defined by weight relative to the total weight of the colloidal stabilizer). According to another embodiment, the emulsifier is an anionic or amphiphilic biopolymer preferably selected from the group consisting of gum arabic, soy protein, gelatin, sodium caseinate, and mixtures thereof.

[0064] According to another embodiment, the shell is a polyurethane-based material, such as, but not limited to, a polyurethane prepared from polyisocyanates and polyols, polyamides, polyesters, and the like.

[0065] The preparation of aqueous dispersions / slurries of core-shell microcapsules is well known to those skilled in the art. In one embodiment, the microcapsule wall material may comprise any suitable resin, particularly melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, and the like. Suitable resins include reaction products of aldehydes and amines, and suitable aldehydes include formaldehyde and glyoxal. Suitable amines include melamine, urea, benzoguanamine, glycoluril, and mixtures thereof. Suitable melamines include methylolmelamine, methylated methylolmelamine, iminomelamine, and mixtures thereof. Suitable ureas include dimethylolurea, methylated dimethylolurea, urea-resorcinol, and mixtures thereof. Suitable materials for manufacturing are available from one or more of the following companies: Solutia Inc. (St. Louis, Missouri USA), Cytec Industries (West Paterson, New Jersey USA), and Sigma-Aldrich (St. Louis, Missouri USA).

[0066] According to certain embodiments, the core-shell microcapsules are formaldehyde-free capsules. A typical method for preparing a formaldehyde-free aminoplast microcapsule slurry comprises: 1) a) a polyamine component in the form of melamine or in the form of a mixture of melamine with at least one C1-C4 compound containing two NH2 functional groups; b) Glyoxal / C 4~6 Glyoxal and 2,2-dialkoxy-ethanal in a molar ratio of 1 / 1 to 10 / 1. 4~6 an aldehyde component in the form of a mixture of 2,2-dialkoxy-ethanal and, optionally, glyoxalate; and c) protonic acid catalyst; preparing an oligomeric composition containing or obtained by reacting together the reaction products of 2) i. oil; ii.Aqueous medium; iii. at least one oligomeric composition obtained in step 1; iv. A) C4~C 12 and / or aromatic or aliphatic diisocyanates or triisocyanates of the formula (I) and their biurets, triuret, trimers, trimethylolpropane adducts, and mixtures thereof; and / or B) Di- or tri-oxirane compounds of the formula: A-(oxiran-2-ylmethyl) n wherein n is 2 or 3, and A is a C2-C6 group optionally containing 2 to 6 nitrogen and / or oxygen atoms. at least one crosslinker selected from the group consisting of v. Optionally, a C1-C4 compound containing two NH2 functional groups; preparing an oil-in-water dispersion, the droplet size of which is comprised between 1 and 600 μm; 3) heating the dispersion; 4) cooling the dispersion; This method is described in detail in WO 2013 / 068255, the contents of which are incorporated by reference.

[0067] According to another embodiment, the shell of the microcapsules is polyurea-based or polyurethane-based. Examples of methods for preparing polyurea-based and polyurethane-based microcapsule slurries are described in, for example, WO 2007 / 004166, EP 2300146, and EP 2579976, the contents of which are also incorporated by reference. Typically, the methods for preparing polyurea-based and polyurethane-based microcapsule slurries include: a) dissolving at least one polyisocyanate having at least two isocyanate groups in oil to form an oil phase; b) preparing an aqueous solution of an emulsifier or colloidal stabilizer to form an aqueous phase; c) adding an oil phase to an aqueous phase to form an oil-in-water dispersion whose average droplet size is comprised between 1 and 500 μm, preferably between 5 and 50 μm; d) applying conditions sufficient to induce interfacial polymerization and form microcapsules in the form of a slurry; Includes:

[0068] In certain embodiments, encapsulation of a compound of formula (I) can provide an environment within the capsule in which all or part of the compound of formula (I) can oxidize, thereby releasing the respective ketone of formula (II), formate of formula (III), or alcohol of formula (IV) within the capsule. In preferred embodiments, the shell of the microcapsule can function as a permeability barrier that prevents the respective ketone of formula (II), formate of formula (III), or alcohol of formula (IV) from leaking out of the capsule.

[0069] In a second aspect, the present invention relates to a method or process for imparting, enhancing, improving or modifying the olfactory characteristics of a perfumed composition, the air surrounding a perfumed composition, a surface, or a perfumed article, comprising adding to the composition, air, or 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 skin, hair, textiles, or hard surface of a user onto which a perfume composition containing at least one compound of formula (I) is applied.

[0070] In a third aspect, the present invention relates to a method for enhancing or prolonging the diffusion effect of the characteristic fragrance of at least one active ketone of formula (II), at least one active formate ester 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 article 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 ester of formula (III), and / or at least one active alcohol of formula (IV).

[0071] In a fourth aspect, the present invention provides a method for producing a medicament for the treatment of a pulmonary arthritis, comprising: i) at least one compound of formula (I) as defined above; ii) at least one ingredient selected from the group consisting of a fragrance carrier and a fragrance base; and iii) optionally at least one flavoring adjuvant; The present invention relates to a fragrance composition comprising:

[0072] By "perfume carrier" is meant herein a material that is substantially neutral from the perfume point of view, i.e., that does not significantly alter the organoleptic properties of the perfuming ingredients. The carrier may be liquid or solid.

[0073] As the liquid carrier, non-limiting examples include emulsifying systems, i.e., systems of solvents and surfactants, or solvents commonly used in perfumery.It is not possible to comprehensively describe the nature and type of solvents commonly used in perfumery.However, non-limiting examples include solvents such as butylene or propylene glycol, glycerol, dipropylene glycol and its monoethers, 1,2,3-propanetriyl triacetate, dimethyl glutarate, dimethyl adipate, 1,3-diacetyloxypropan-2-yl acetate, diethyl phthalate, isopropyl myristate, benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethanoate, triethyl citrate, or mixtures thereof, which are the most commonly used. For compositions comprising both a perfume carrier and a perfume base, suitable perfume carriers other than those defined above may be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar® (supplied by Exxon Chemical), or glycol ethers and glycol ether esters such as those known under the trademark Dowanol® (supplied by Dow Chemical Company), or hydrogenated castor oils such as those known under the trademark Cremophor® RH 40 (supplied by BASF).

[0074] Solid carrier is intended to refer to a material that can chemically or physically bind perfume composition or some components of perfume composition.Generally, such solid carrier is used to stabilize composition or control the evaporation rate of composition or some components.The use of solid carrier is currently used in the art, and those skilled in the art know how to achieve the desired effect.However, non-limiting examples of solid carrier can include absorbent gum or polymer or inorganic material, such as porous polymer, cyclodextrin, wood-based material, organic or inorganic gel, clay, gypsum talc, or zeolite.

[0075] Other non-limiting examples of solid carriers can include encapsulating materials.Examples of such materials can include wall-forming and plasticizing materials such as monosaccharides, disaccharides, or trisaccharides, natural or modified starch, hydrocolloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, protein, or pectin, or can include materials listed in reference texts such as H. Scherz, Hydrokolloides: Stabilisatoren, Dickungs- und Geliermittel in Lebensmitteln, Band 2 der Schriftenreihe Lebensmittelchemie, Lebensmittelqualitaet, Behr's Verlag GmbH & Co., Hamburg, 1996.Encapsulation is a process well known to those skilled in the art, and can be carried out by using techniques such as spray drying, coagulation, or even extrusion; or can be comprised of coating encapsulation, such as coacervation and complex coacervation techniques.

[0076] Non-limiting examples of solid carriers include core-shell capsules using aminoplast, polyamide, polyester, polyurea, or polyurethane type resins or mixtures thereof (all of which are well known to those skilled in the art) using techniques such as phase separation processes induced by polymerization, interfacial polymerization, coacervation, or all together, optionally in the presence of polymeric stabilizers or cationic copolymers (all of which are described in the prior art).

[0077] The resins can be prepared by polycondensation of aldehydes (e.g., formaldehyde, 2,2-dimethoxyethanal, glyoxal, glyoxylic acid, or glycolaldehyde, and mixtures thereof) with amines such as urea, benzoguanamine, glycoluril, melamine, methylolmelamine, methylated methylolmelamine, guanazole, and the like, and mixtures thereof. Alternatively, alkylolated polyamines can be used that are preformed resins, such as those commercially available under the trademarks Urac® (supplied by Cytec Technology Corp.), Cy mel® (supplied by Cytec Technology Corp.), Urecoll®, or Luracoll® (supplied by BASF).

[0078] Other resins are those obtained by polycondensation of a polyol such as glycerol with a polyisocyanate such as the trimer of hexamethylene diisocyanate, isophorone diisocyanate or xylylene diisocyanate, or the biuret of hexamethylene diisocyanate, or the trimer of xylylene diisocyanate, and trimethylolpropane (known under the trademark Takenate®; supplier: Mitsui Chemicals), especially the trimer of xylylene diisocyanate, trimethylolpropane, and the biuret of hexamethylene diisocyanate.

[0079] Some influential publications on the encapsulation of perfumes by the polycondensation of amino resins, i.e., melamine-based resins with aldehydes, are represented by articles such as K. Dietrich et al., Acta Polymerica, 1989, Vol. 40, pages 243, 325, and 683, and 1990, Vol. 41, page 91. Such articles already describe the various parameters that affect the production of such core-shell microcapsules according to prior art methods, which are further explained and exemplified in the patent literature. U.S. Patent No. 4,396,670 to Wiggins Teape Group Limited is an early example of the latter. Since then, many other authors have enriched the literature in this field, and it would be impossible to cover all published developments here, but a basic understanding of encapsulation technology is very important. Suitable more recent publications disclosing suitable uses of such microcapsules include, for example, the articles by H.Y. Lee et al. in Journal of Microencapsulation, 2002, vol. 19, pages 559-569 and International Patent Application No. 01 / 41915, as well as the article by S. Bone et al. in Chimia, 2011, vol. 65, pages 177-181.

[0080] The term "perfume base" is understood as a composition containing at least one perfuming co-ingredient.

[0081] Perfuming co-ingredients are not compounds according to the present invention. Furthermore, the term "perfuming co-ingredients" is understood as compounds used in perfume formulations or compositions to provide a hedonic effect. In other words, a co-ingredient that is considered to be perfuming must not only have an odor, but must also be recognized by those skilled in the art as being able to provide or modify the odor of the composition in a positive or pleasant way.

[0082] The nature and type of perfuming co-ingredients present in the base are not warranted in this specification in any way, and are in any way not exhaustive, but can be selected by a person skilled in the art based on his basic knowledge and depending on the intended use or application and the desired organoleptic effect. Generally, these perfuming co-ingredients belong to various chemical classes, such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpene hydrocarbons, nitrogen or sulfur heterocyclic compounds, and essential oils, and they may be of natural or synthetic origin.

[0083] Mention may in particular be made of perfuming co-ingredients known to have similar olfactory notes, such as: Mention may be made in particular of the perfuming co-ingredients commonly used in perfume formulations, such as: - aldehyde components: decanal, dodecanal, 2-methyl-undecanal, 10-undecenal, octanal, and / or nonenal; - Aromatic herbal ingredients: eucalyptus oil, camphor, eucalyptol, menthol, and / or alpha-pinene; - Balsam ingredients: coumarin, ethyl vanillin, and / or vanillin; - Citrus ingredients: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellyl nitrile, orange terpenes, limonene, 1-P-menthen-8-yl acetate, and / or 1,4(8)-P-menthadiene; - Floral Ingredients: Methyl Dihydrojasmonate, Linalool, Citronellol, Phenylethanol, 3-(4-tert-butylphenyl)-2-methylpropanal, Hexyl Cinnamaldehyde, Benzyl Acetate, Benzyl Salicylate, Tetrahydro-2-Isobutyl-4-methyl-4(2H)-pyranol, Beta-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, Versyl Acetate, Geraniol, P-Menth-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, high-cis methyl dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol, vergyl proprionate, geranyl acetate, tetrahydrolinalool, cis-7-p-menthanol, propyl (S)-2-(1,1-dimethylpropoxy)propanoate, 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, vergyl isobutyrate, and / or methyl ionone isomeric mixture; - Fruity ingredients: gamma undecalactone, 4-decanolide, ethyl 2-methylpentanoate, hexyl acetate, ethyl 2-methylbutanoate, gamma nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-acetate, and / or diethyl 1,4-cyclohexanedicarboxylate; - Green ingredients: 2,4-dimethyl-3-cyclohexene-1-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styrallyl acetate, allyl (2-methylbutoxy) 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; - Musk ingredients: 1,4-dioxa-5,17-cycloheptadecanedione, pentadecenolide, 3-methyl-5-cyclopentadecen-1-one, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-g-2-benzopyran, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropylpropanoate, pentadecanolide, and / or (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methylpropanoate; - Woody ingredients: 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-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; Other ingredients (e.g., amber, powdery spicy, or watery): dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1-b]furan and any stereoisomers thereof, heliotropin, anisaldehyde, eugenol, cinnamaldehyde, clove oil, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal, and / or 3-(3-isopropyl-1-phenyl)butanal.

[0084] The perfume base according to the present invention may not be limited to the above-mentioned perfuming co-ingredients, many of which are described in reference texts such as S. Arctander, *Perfume and Flavor Chemicals*, 1969, Montclair, New Jersey, USA, or its later editions, or other works of a similar nature, and in the abundant patent literature in the field of perfumery. It is also understood that the co-ingredients may be compounds known to provide controlled release of various types of perfuming compounds.

[0085] The term "perfuming adjuvant" is understood as an ingredient that can provide additional benefits such as color, specific light resistance, chemical stability, etc. Although a detailed description of the nature and type of adjuvants commonly used in perfume bases cannot be exhaustive, it should be mentioned that the ingredients are well known to those skilled in the art. However, specific, non-limiting examples include viscosity agents (e.g., surfactants, thickeners, gelling agents, and / or rheology modifiers), stabilizers (e.g., preservatives, antioxidants, heat / light and / or buffering agents or chelating agents, e.g., BHT), colorants (e.g., dyes and / or pigments), preservatives (e.g., antibacterial or antimicrobial or antifungal or anti-irritant agents), abrasives, skin cooling agents, fixatives, insect repellents, ointments, vitamins, and mixtures thereof.

[0086] It will be understood that a person skilled in the art is fully capable of designing the optimum formulation for the desired effect by simply applying standard knowledge in the art and by trial and error methodology by mixing the above-mentioned components of the perfume composition.

[0087] The composition of the present invention, which comprises at least one compound of formula (I) of the present invention and at least one perfume carrier, represents a particular embodiment of the present invention and represents a perfume composition containing at least one compound of the present invention, at least one perfume carrier, at least one perfume base, and optionally at least one perfume adjuvant.

[0088] It is useful to mention here that the possibility of having more than one compound of the invention or other precursors of the same type in the compositions described above is important as it allows the perfumer to prepare accords and fragrances with the olfactory tonality of the various compounds of the invention, thus forming new building blocks for creative purposes.

[0089] For the sake of clarity, it is also understood that any mixture resulting directly from a chemical synthesis, such as an insufficiently purified reaction medium that may contain a compound of the invention as a starting material, intermediate, or final product, cannot be considered a perfuming composition according to the invention, unless the mixture provides the compound of the invention in a form suitable for perfumery.Unless otherwise specified, unpurified reaction mixtures are therefore generally excluded from the present invention.

[0090] Furthermore, the compounds of the present invention can also be advantageously used in any field of modern perfumery, i.e., premium or functional perfumery, to positively impart or modify the odor of consumer products to which compound (I) is added.

[0091] Therefore, in a fifth aspect, the present invention relates to a perfumed consumer product containing at least one compound of formula (I) as defined above or a perfuming composition as defined above.

[0092] For the sake of clarity, it should be mentioned that the term "perfumed consumer product" is understood as a consumer product that is expected to provide at least a pleasant fragrance effect to a surface to which it is applied (e.g., skin, hair, textiles, or hard surfaces). In other words, the perfumed consumer product according to the present invention is a perfumed consumer product that contains a functional formulation, as well as an optional additional benefit agent corresponding to the desired consumer product, such as a conditioner, detergent, or deodorant, and an olfactory-effective amount of at least one compound of the present invention. For the sake of clarity, it should be mentioned that the perfumed consumer product is a non-edible product.

[0093] The nature and type of ingredients of perfumed consumer products do not warrant a more detailed description herein, which is in any case not considered to be exhaustive, and which a person skilled in the art can select based on his general knowledge and the nature of the product and the desired effect.

[0094] In certain embodiments, the perfumed consumer product is a fragrance, a fabric care product, a body care product, a cosmetic, a skin care product, an air care product, or a home care product.

[0095] Non-limiting examples of suitable perfumed consumer products include perfumes such as fine perfumes, splashes or eau de perfumes, colognes or shave or aftershave lotions; 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 hairsprays, color care products, hair styling products, dental care products), disinfectants, intimate care products; cosmetics (e.g. skin creams or lotions, vanishing creams or deodorants or antiperspirants (e.g. sprays or roll-ons), hair removal products, tanning or sunscreen or after-sun products, nail products, skin cleansing, cosmetics); or skin care products (e.g. soaps, shower or bath mousses, oils, or gels, or hygiene or foot / hand care products); air care products such as deodorants or "ready-to-use" powdered air fresheners that can be used in domestic spaces (rooms, refrigerators, cupboards, shoes, or cars) and / or public spaces (hall, hotel, mall, etc.); or home care products such as mold removers, furniture care products, wipes, dish detergents, or hard surface (e.g. floor, bathroom, toilet, or window cleaner) cleaners; leather care products; car care products such as polishes, waxes, or plastic cleaners.

[0096] Typical examples of laundry detergent or fabric softener compositions that can incorporate the compounds of the present invention are described in International Publication No. 97 / 34986, U.S. Patent Nos. 4,137,180 and 5,236,615, or European Patent No. 799885. Other typical detergent and fabric softener compositions that can be used are described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 20, Wiley-VCH, Weinheim, pp. 355-540 (2012); Flick, Advanced Cleaning Product Formulations, Noye Publication, Park Ridge, New Jersey (1989); Showell, in Surfactant Science Series, Vol. 71: Powdered Detergents, Marcel Dekker, New York (1988); Proceedings of the World Conference on Detergents (4th, 1998, Montreux, Switzerland), AOCS print, and other publications.

[0097] The proportions in which the compounds according to the invention can be incorporated into the various articles or compositions mentioned above vary within a wide range of values, depending on the nature of the article or product to be perfumed, the olfactory effect desired, and the nature of the co-ingredients in a given composition when the compounds according to the invention are mixed with perfuming co-ingredients, solvents or additives commonly used in the art.

[0098] For example, typical concentrations are from 0.001% to 10% by weight or more of the compounds of the present invention based on the weight of the composition to be formulated in. When these compounds are used directly to perfume or flavor the various consumer products mentioned above, lower concentrations, such as from 0.001% to 5% by weight, can be used.

[0099] In a sixth aspect, the present invention provides a compound of formula (I): [ka] [In the formula, R1 is C 1~8 Alkyl, C 1~8 Alkoxy, carboxylic acid, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~15 Alkyl, C 1~15 Alkoxy, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 6~10 aryl, and / or C 6~10 C, each optionally substituted with one or more aryloxy groups 1~15 Alkyl, C 2~15 Alkenyl, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, or C 6~10 represents an aryl group; R2 is C 1~15 represents an alkyl group; R1 and R2, when taken together, are C 1~8 Alkyl, C 1~8 Alkoxy, carboxylic acid, 4-methylcyclohex-3-en-1-yl, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 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 C, each optionally substituted with one or more aryloxy groups 5~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 4~14 Heterocycloalkyl, or C 4~14 forming heterocycloalkenyl groups, the heteroatoms of which represent one or more oxygens; R3 is C 1~8 Alkyl, C 1~8 Alkoxy, carboxylic acid, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~15 Alkyl, C 1~15 Alkoxy, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 6~10 aryl, and / or C 6~10 C, each optionally substituted with one or more aryloxy groups 1~15 Alkyl, C 2~15 Alkenyl, C 3~15 Cycloalkyl, or C 5~15 represents a cycloalkenyl group; R4 is independently hydrogen or C 1~5 represents an alkyl group; R1 and R4, when taken together, are C 1~8 Alkyl, C 1~8 Alkoxy, carboxylic acid, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~15 Alkyl, C 1~15 Alkoxy, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 6~10 aryl, and / or C 6~10 C, each optionally substituted with one or more aryloxy groups 3~15 Cycloalkyl or C 5~15 forming a cycloalkenyl group; R3 and R4, when taken together, are C 1~8 Alkyl, C 1~8 Alkoxy, carboxylic acid, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~15 Alkyl, C 1~15 Alkoxy, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, C6~10 aryl, and / or C 6~10 C, each optionally substituted with one or more aryloxy groups 3~15 Cycloalkyl or C 5~15 forming a cycloalkenyl group]; and C 16 ~C 28 Although it is a compound, - If R1 is a methyl group, R2 is neither a methyl group nor an ethyl group, - If R1 is an ethyl group, R2 is not an ethyl group, - When R3 is an unsubstituted methyl group, R4 is neither a hydrogen atom nor a methyl group, - when R3 is an unsubstituted ethyl group, R4 is not a hydrogen atom; and the following compounds: (((3,7-dimethylocta-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'-ethylhexoxy)-2-ethyl-1,3-hexadiene, 1-((2-methylpent-1-en-1-yl)oxy)dodecane, 3-(cyclohexylidenemethoxy)-1,5,5-trimethylcyclohex-1-ene, (3-(benzyloxy)-2-methylallyl)benzene, and 4-(4-(allyloxy)-3-methylbut-3-en-1-yl)-1,2-dimethoxybenzene, This relates to compounds of formula (I), with the proviso that:

[0100] Exemplary embodiments of compounds of Formula (I) are described above.

[0101] In a preferred embodiment, the following moiety of formula (I) [ka] corresponds to the ketone of formula (II) as defined above. In a preferred embodiment, the following moiety of formula (I) [ka] corresponds to the alcohol of formula (IV) defined above.

[0102] In a further aspect, the present invention also relates to microcapsules containing 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, in which at least one compound of formula (I) is contained in a core surrounded by a shell. In a preferred embodiment, the shell of the microcapsule protects the compound of formula (I) from the environment. The shell is made of a material capable of releasing at least one compound of formula (I) and / or compounds of formulas (II), (III), and / or (IV). In a preferred embodiment, the shell is made of a material capable of releasing the compound of formula (I) and / or compounds of formulas (II), (III), and / or (IV) upon rupture of the shell and / or by diffusion through the shell. Those skilled in the art are well aware of methods for producing such microcapsules.

[0103] In a further aspect, the present invention provides a method for producing a pharmaceutical composition comprising: a) a ketone of formula (II) [ka] [In the formula, R1 is C 1~8 Alkyl group, C 1~8 Alkoxy, hydroxy, carboxylic acid groups, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~15 Alkyl, C 1~15 Alkoxy, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 6~10 aryl, and / or C 6~10 C, each optionally substituted with one or more aryloxy groups 1~15 Alkyl, C 2~15 Alkenyl, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl group, or C 6~10 represents aryl; R2 is C 1~15 represents an alkyl group; R1 and R2, when taken together, are C 1~8 Alkyl, C 1~8 Alkoxy, carboxylic acid, 4-methylcyclohex-3-en-1-yl, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 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 C, each optionally substituted with one or more aryloxy groups 5~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 4~14 Heterocycloalkyl, or C 4~14 forming heterocycloalkenyl groups, the heteroatoms of which represent one or more oxygens; R4 is independently hydrogen or C 1~5 represents an alkyl group; R1 and R4, when taken together, are C 1~8 Alkyl, C 1~8 Alkoxy, carboxylic acid, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~15 Alkyl, C 1~15 Alkoxy, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 6~10 aryl, and / or C 6~10 C, each optionally substituted with one or more aryloxy groups 3~15 Cycloalkyl or C 5~15 forming a cycloalkenyl group]; b) a formate ester of formula (III) [ka] [In the formula, R3 is C 1~8 Alkyl, C 1~8 Alkoxy, carboxylic acid, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~15 Alkyl, C 1~15 Alkoxy, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 6~10 aryl, and / or C 6~10 C, each optionally substituted with one or more aryloxy groups 1~15 Alkyl, C 2~15 Alkenyl, C 3~15 Cycloalkyl, or C 5~15 represents a cycloalkenyl group; R4 has the same meaning as defined above; R3 and R4, when taken together, are C 1~8 Alkyl, C 1~8 Alkoxy, carboxylic acid, and / or C 1~4 C, each optionally substituted with one or more carboxylic acid ester groups 1~15Alkyl, C 1~15 Alkoxy, C 3~15 Cycloalkyl, C 5~15 Cycloalkenyl, C 6~10 aryl, and / or C 6~10 C, each optionally substituted with one or more aryloxy groups 3~15 Cycloalkyl or C 5~15 forming a cycloalkenyl group]; c) an alcohol of formula (IV) [ka] wherein R3 and R4 have the same meanings as defined above; 1. Use of a precursor compound to release a compound selected from the group consisting of: at least one of the compounds of formula (II), (III), or (IV) is the active compound; The precursor is a compound of formula (I) [ka] [wherein R1, R2, R3, and R4 have the same meanings as defined above]; wherein said release occurs by placing the precursor compound in an environment where it is oxidized.

[0104] In a further aspect, the present invention relates to the use of at least one compound of formula (I) as defined above for imparting, enhancing, improving or modifying the odour characteristics of a perfume composition, the air surrounding the perfume composition, a surface or a perfumed article, comprising adding to the composition or article an effective amount of at least one compound of formula (I) as defined above, or contacting or treating a 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 skin, hair, textiles or hard surface of a user onto which a perfume composition containing at least one compound of formula (I) is applied.

[0105] In a further 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 formate ester of formula (III), and / or at least one alcohol of formula (IV) as defined above on a surface, wherein the surface is treated with at least one compound of formula (I) as defined above or with a composition or article containing at least one compound of formula (I) under conditions allowing the release over time of at least one active ketone of formula (II), at least one formate ester of formula (III), and / or at least one active alcohol of formula (IV).

[0106] Example 1. Compound synthesis The following compounds were synthesized and characterized. Unless otherwise stated, mass spectral data (EI, 70 eV), major fragment ions and relative abundances, and NMR data are shown only for the E-isomer (usually the major isomer). NMR spectra were recorded using CDCl3 as the solvent. Chemical shifts δ are given in ppm relative to TMS as the reference, and coupling constants J are in Hz.

[0107] Examples 1 to 6 A 25 mL round-bottom flask equipped with a distillation head and nitrogen bubbler was charged with dimethyl acetal (35 mmol), alcohol (70 mmol), and KHSO (48 mg, 0.35 mmol). The mixture was heated (oil bath at 150 °C) while distilling off the liberated methanol (vapor temperature 64 °C) until a drop in vapor temperature (40–60 min) indicated that most of the methanol had been removed. The mixture was placed under vacuum (300 mTorr) and heated (oil bath at 180–190 °C) for 2–3 h while the liberated alcohol distilled from the reaction flask. The enol ether was isolated by vacuum distillation from the reaction flask after the addition of NaCO (0.5 g) or by silica gel flash chromatography followed by Kugelrohr distillation.

[0108] Example 1. (2-((2-methylundec-1-en-1-yl)oxy)ethyl)benzene: Starting from the dimethyl acetal of 2-methylundecanal and 2-phenylethanol, the title compound was isolated as a colorless oil in 91% yield by distillation (bp 130°C, 30 mTorr) (E / Z=59:41). [ka]

[0109] Example 2. (2-((2-methylundec-1-en-1-yl)oxy)ethoxy)benzene: Starting from the dimethyl acetal of 2-methylundecanal and 2-phenoxyethanol, the title compound was isolated as a colorless oil in 90% yield by distillation (bp 128-130°C, 25 mTorr) (E / Z=60:40). [ka]

[0110] Example 3. (3-methyl-4-phenethoxybut-3-en-1-yl)benzene: Starting from the dimethyl acetal of 2-methyl-4-phenylbutanal and 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). [ka]

[0111] Example 4. 1-Methoxy-4-(2-methyl-3-phenethoxyallyl)benzene: Starting from the dimethyl acetal of 3-(4-methoxyphenyl)-2-methylpropanal and 2-phenylethanol, the title compound was isolated as a colorless oil in 77% yield by distillation (bp 155-158°C, 30 mTorr) (E / Z=56:44). [ka]

[0112] Example 5. (2-((2-methyl-4-(2,6,6-trimethylcyclohex-1-en-1-yl)but-1-en-1-yl)oxy)ethyl)benzene: Starting from the dimethyl acetal of 2-methyl-4-(2,6,6-trimethylcyclohex-1-en-1-yl)butanal and 2-phenylethanol, the title compound was isolated as a colorless oil in 74% yield (E / Z=45:55) by silica gel flash chromatography (hexane / EtOAc, 98:3) followed by Kugelrohr distillation (180 °C, 30 mTorr). [ka]

[0113] Example 6. (2-((2,2,6-trimethylcyclohexylidene)methoxy)ethyl)benzene Starting from the dimethyl acetal of 2,2,6-trimethylcyclohexane-1-carbaldehyde and 2-phenylethanol, the title compound was isolated as a light brown oil in 70% yield (E / Z=76:24) by silica gel flash chromatography (hexane / EtOAc, 98:2) followed by Kugelrohr distillation (130-150 °C, 40 mTorr). [ka]

[0114] Examples 7-8 A solution of aldehyde (30–25 mmol), 1-octanol (2.5 equiv.), and TsOH (0.02 equiv.) in toluene (100 mL) was heated to reflux for 2–3 h. A Dean-Stark trap was used to remove the water of reaction. 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 equiv.) and heated at 180 °C under reduced pressure (35 Torr) using a Kugelrohr distillation apparatus for 1–2 h. The remaining residue was then subjected to Kugelrohr distillation to give the enol ether (typical conditions: 140–170 °C, 50 mTorr).

[0115] Example 7. 2-Methyl-1-(octyloxy)undec-1-ene: Starting from 2-methylundecanal, the title compound was isolated as a colorless liquid in 53% yield (E / Z=50:50). [ka]

[0116] Example 8. (3-methyl-4-(octyloxy)but-3-en-1-yl)benzene: Starting from 2-methyl-4-phenylbutanol, the title compound was isolated as a colorless liquid in 57% yield (E / Z=58:42). [ka]

[0117] Example 9. 1-Methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene: 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 t-butoxide (6.18 g, 55.1 mmol) was added to the stirred slurry in four portions every 15 minutes. The mixture was stirred for an additional 4 hours, during which time it became a pale yellow, homogeneous solution. It was then poured into 200 mL of water and extracted with diethyl 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 / CHCl1 100:0 → 75:25) to afford 4.06 g (19.7 mmol) of the methyl enol ether product. This material (3.8 g, 18.4 mmol) was combined with 2-phenylethanol (4.5 g, 36.8 mmol) and KHSO (0.027 g, 0.198 mmol) in a round-bottom flask (25 mL) equipped with a distillation head and nitrogen bubbler. The mixture was heated at 150 °C for 1 hour, and the liberated methanol was distilled from the mixture. The mixture was then placed under reduced pressure (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). [ka]

[0118] Examples 10 to 14. A solution of aldehyde (30–25 mmol), 3-octanol (2.5 equiv.), and TsOH (0.02 equiv.) in toluene (100 mL) was heated to reflux for 3–4 h. A Dean-Stark trap was used to remove the water of reaction. 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 first to remove excess 3-octanol (typical conditions: 90 °C, 50 mTorr) and then to obtain the enol ether (typical conditions: 140–170 °C, 50 mTorr).

[0119] Example 10. 2-Methyl-1-(octan-3-yloxy)undec-1-ene: Starting from 2-methylundecanal, the title compound was isolated as a colorless oil in 46% yield (E / Z=61:39). [ka]

[0120] Example 11. (3-methyl-4-(octan-3-yloxy)but-3-en-1-yl)benzene: Starting from 2-methyl-4-phenylbutanal, the title compound was isolated as a colorless oil in 56% yield (E / Z=58:42). [ka]

[0121] Example 12. 1-Methoxy-4-(2-methyl-3-(octan-3-yloxy)allyl)benzene: Starting from 3-(4-methoxyphenyl)-2-methylpropanal, the title compound was isolated as a colorless oil in 53% yield (E / Z=59:41). [ka]

[0122] Example 13. 1,3,3-trimethyl-2-(3-methyl-4-(octan-3-yloxy)but-3-en-1-yl)cyclohex-1-ene: Starting from 2,2,6-trimethylcyclohexane-1-carbaldehyde, the title compound was isolated as a colorless oil in 38% yield after two successive Kugelrohr distillations (E / Z=50:50). [ka]

[0123] Example 14. ((2-methylundec-1-en-1-yl)oxy)cyclododecane: 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 h while removing water of reaction with a Dean-Stark trap. After cooling, the mixture 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 subjected to Kugelrohr distillation (160-180 °C, 50 mTorr) to afford 2.54 g of the title compound (7.24 mmol, 32% yield) as a colorless oil (E / Z = 55:45). [ka]

[0124] Example 15. 1-((2,6-dimethyloct-7-en-2-yl)oxy)-2-methylundec-1-ene: A hexane solution (100 mL) of 2-methylundecanal (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 h while removing water of reaction with a Dean-Stark trap. The mixture was diluted with additional hexane and washed with saturated NaHCO3 and saturated brine. The organic phase was dried over Na2SO4, filtered, and concentrated. After adding Na2CO3 (1 g), the residue was subjected to short-path distillation (bp 138 °C, 30 mTorr) to give 2.2 g of the title compound (6.82 mmol, 8% yield) as a colorless oil (E / Z = 61:39). [ka]

[0125] Example 16. 1-(((Z)-hex-3-en-1-yl)oxy)-2-methylundec-1-ene: A 100 mL round-bottom flask equipped with a Vigreux column (12 cm), distillation head, and nitrogen bubbler was charged with the dimethyl acetal of 2-methylundecanal (20 g, 87 mmol), cis-3-hexen-1-ol (26.1 g, 260 mmol), and KHSO (0.118 g, 0.87 mmol). The mixture was heated at 150 °C for 1 hour while the liberated methanol was distilled off. The Vigreux column was removed, and heating was continued at 190 °C for 1 hour while the liberated cis-3-hexen-1-ol was distilled from the reaction flask. The mixture was allowed to cool, placed under reduced pressure (5 Torr), and heated at 130 °C for 3 hours to remove the remaining hexenol. The enol ether was then isolated from the reaction flask by vacuum distillation (bp 120–130°C, 25 mTorr) followed by Kugelrohr distillation (115°C, 25 mTorr) to give the title compound (17.0 g, 63.8 mmol) as a colorless liquid in 73% yield (E / Z = 56:44). [ka]

[0126] Examples 17-19. Dimethyl acetal (35-60 mmol), alcohol (2 equivalents mmol), and KHSO4 (48 mg, 0.35 mmol) were placed in a 25-50 mL round-bottom flask equipped with a distillation head and nitrogen bubbler. The mixture was heated (oil bath at 150 °C) while distilling off the liberated methanol (vapor temperature 64 °C) until the vapor temperature dropped (40-60 min), indicating that most of the methanol had been removed. The mixture was placed under vacuum (300-500 mTorr) and heated (oil bath at 180-190 °C) for 2-3 h while the liberated alcohol was distilled from the reaction flask. The enol ether was isolated by vacuum distillation from the reaction flask after the addition of Na2CO3 (0.25 g-0.5 g) or by silica gel flash chromatography followed by Kugelrohr distillation.

[0127] Example 17. (2-((2-methyldec-1-en-1-yl)oxy)ethyl)benzene: Starting from the dimethyl acetal of 2-methyldecanal and 2-phenylethanol, the title compound was isolated by distillation (bp 140-150°C, 20 mTorr) as a slightly yellowish oil in 86% yield (E / Z=60:40). [ka]

[0128] Example 18. 1-((3,7-dimethyloct-6-en-1-yl)oxy)-2-methylundec-1-ene: Starting from the dimethyl acetal of 2-methylundecanal and citronellol, the title compound was isolated by distillation (bp 160°C, 50 mTorr) as a pale yellow oil in 83% yield (E / Z=58:42). [ka]

[0129] Example 19. (2-((2-ethylhex-1-en-1-yl)oxy)ethyl)benzene: Starting from the dimethyl acetal of 2-ethylhexanal and 2-phenylethanol, the title compound was isolated as a pale yellow oil by distillation (bp 140-145°C, 500 mTorr) in 77% yield (E / Z=57:43). [ka]

[0130] Examples 20 to 29. Methoxymethyltriphenylphosphonium chloride (15.1 g, 44.1 mmol) and the ketone (29.4 mmol) were added to 120 mL of toluene. Potassium t-butoxide (5.27 g, 47 mmol) was added to the stirred slurry in four portions every 15 minutes. The mixture was stirred for 4 hours, turning deep red. It was then poured into 500 mL of water and extracted with EtOAc (3 × 250 mL). The organic phases were combined, dried over NaSO, filtered, and concentrated. The resulting methyl enol ether product was isolated by flash chromatography (silica gel, hexane) followed by Kugelrohr distillation. The methyl enol ether (30–60 mmol) was then combined with 2-phenylethanol (2 equiv.) and KHSO (1 mol%) in a round-bottom flask (50 mL) equipped with a distillation head and nitrogen bubbler. The mixture was heated (oil bath at 150°C) while distilling off liberated methanol (vapor temperature 64°C) until the vapor temperature decreased (typically 40 min). The mixture was then placed under vacuum (300 mTorr) and heated at 180°C while excess 2-phenylethanol distilled from the flask (typically 2 h). The resulting enol ether was isolated by vacuum distillation from the reaction flask after addition of NaCO (0.25 g) or by silica gel flash chromatography. Product yields are reported for the conversion of the intermediate methyl enol ether to the isolated product.

[0131] Example 20. (Phenethoxymethylene)cyclopentadecane: The title compound was synthesized starting from cyclopentadecanone, which was isolated as a colorless oil in 45% yield from the intermediate methyl enol ether by short-path distillation (bp >170 °C, 25 mTorr) from the crude reaction mixture. [ka]

[0132] Example 21. (2-((4-(tert-pentyl)cyclohexylidene)methoxy)ethyl)benzene: The title compound was synthesized starting from 4-(tert-pentyl)cyclohexan-1-one, which was isolated from the intermediate methyl enol ether in 24% yield as a colorless oil by silica gel flash chromatography (hexane / EtOAc, 100:0 to 95:5). [ka]

[0133] Example 22. 9-(Phenethoxymethylene)cyclododeca-1,5-diene: The title compound was synthesized starting from cyclododeca-4,8-dien-1-one (a mixture of E,E-, E,Z-, and Z / E isomers), which was isolated from the intermediate methyl enol ether by short-path distillation (bp 172 °C, 30 mTorr) from the crude reaction mixture as a colorless oil in 83% yield (mixture of stereoisomers). [ka]

[0134] Example 23. (1SR,4RS,4aSR,8aRS)-6-methyl-7-(phenethoxymethylene)decahydro-1,4-methanonaphthalene: The title compound was synthesized starting from (1RS,4SR,4aRS,8aSR)-7-methyloctahydro-1,4-methanonaphthalen-6(2H)-one. It was isolated from the intermediate methyl enol ether by short-path distillation (bp 165-170 °C, 15 mTorr) from the crude reaction mixture followed by Kugelrohr distillation (oven 150 °C, 25 mTorr) as a pale yellow oil in 58% yield (mixture of stereoisomers). [ka]

[0135] Example 24. (2-(((2RS,5SR)-2-isopropyl-5-methylcyclohexylidene)methoxy)ethyl)benzene: The title compound was synthesized starting from 2-isopropyl-5-methylcyclohexan-1-one (80% trans isomer), which was isolated from the intermediate methyl enol ether by short-path distillation (bp 130-135 °C, 15 mTorr) from the crude reaction mixture as a pale yellow oil in 72% yield (E / Z = 60:40). [ka]

[0136] Example 25. (2-((2-(2-((R)-4-methylcyclohex-3-en-1-yl)propyl)cyclopentylidene)methoxy)ethyl)benzene: The title compound was synthesized starting from 2-(2-((R)-4-methylcyclohex-3-en-1-yl)propyl)cyclopentan-1-one (four diastereomers). It was isolated from the intermediate methyl enol ether by Kugelrohr distillation (oven 220-225 °C, 20 mTorr) from the crude reaction mixture as a colorless oil in 70% yield (mixture of stereoisomers). [ka]

[0137] Example 26. (2-((2-pentylcyclopentylidene)methoxy)ethyl)benzene: The title compound was synthesized starting from 2-pentylcyclopentan-1-one, which was isolated from the intermediate methyl enol ether by Kugelrohr distillation (oven 160-180 °C, 20 mTorr) from the crude reaction mixture as a colorless oil in 88% yield (E / Z = 62:38). [ka]

[0138] Example 27. (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene: The title compound was synthesized starting from 2-heptylcyclopentan-1-one, which was isolated from the intermediate methyl enol ether by Kugelrohr distillation (oven 195-200 °C, 20 mTorr) from the crude reaction mixture as a colorless oil in 87% yield (E / Z = 62:38). [ka]

[0139] Example 28. (2-((2-ethyl-4,4-dimethylcyclohexylidene)methoxy)ethyl)benzene: The title compound was synthesized starting from 2-ethyl-4,4-dimethylcyclohexan-1-one, which was isolated from the intermediate methyl enol ether by Kugelrohr distillation (oven 140-145 °C, 20 mTorr) from the crude reaction mixture as a pale yellow oil in 89% yield (E / Z = 91:9). [ka]

[0140] Example 29. (2-((2-ethyl-4-methylhex-1-en-1-yl)oxy)ethyl)benzene: The title compound was synthesized starting from 5-methylheptan-3-one, which was isolated from the intermediate methyl enol ether by short-path distillation from the crude reaction mixture as a pale yellow oil in 66% yield (isomer ratio = 58:42). [ka]

[0141] 2. Headspace analysis from fabric softener applications A model liquid fabric softener was prepared by mixing 12.3 wt% TEA-esterquat (Stepantex® VL90A), 0.4 wt% 10% aqueous calcium chloride solution, 0.04 wt% Proxcel GXL, and 87.2 wt% deionized water. The enol ether (0.075 mmol) was weighed into a vial and dissolved in 0.25 mL of acetone. Liquid fabric softener (4.5 g) was added to the vial, and the mixture was mixed by hand shaking. A reference sample was prepared in the same manner using 0.075 mmol of each released volatile. The fabric softener sample was rinsed with deionized water and placed in a 3 L beaker, which was filled to a total volume of 1.5 L. Three 5 g cotton swatches (approximately 12.5 x 12.5 cm, weighing 270 g / m) were weighed and dissolved in 0.25 mL of acetone. 2 (Product No. 403, Testfabrics, West Pittston, PA) was placed in a beaker and manually stirred for 3 minutes. After an additional 2 minutes, the swatch was removed and excess water was manually squeezed out. The fabric was hung to dry overnight (15-16 hours) at room temperature. Dynamic headspace analysis was then performed on the swatch.

[0142] Each swatch was placed in a thermostated (25°C) headspace sampling cell (approximately 160 mL volume). Using an air sampling pump, a constant flow of air (200 mL / min) was passed through the sampling cell and then through a cartridge containing 100 mg of Tenax® (waste cartridge). To maintain a constant relative humidity of 75%, air was drawn through a plug of activated charcoal and then through a saturated NaCl solution before entering the sample cell. Headspace samples were collected after 1 and 2 hours by exchanging the waste cartridge for a clean Tenax® cartridge for 15 minutes. The cartridges were thermally desorbed using a Perkin Elmer TurboMatrix 650 thermal desorption unit attached to an Agilent 6890 gas chromatograph equipped with an Agilent 5975C mass spectrometer and a Varian VF-1ms capillary column (30 m, 0.25 μm internal diameter, 0.25 μm membrane). The desorption parameters were: valve temperature 250°C, transfer line 250°C, purge time 1 min, desorption temperature 240°C, desorption time 5 min, desorption flow rate 20 mL / min, trap temperature -30°C to 250°C at 40°C / sec, trap hold time 4 min, outlet split 48 mL / min, and column flow rate 1 mL / min. The GC oven temperature profile was ramped at 20°C / min from 60°C (1 min) to 210°C, then to 250°C (2 min). For the analysis of Pipol, the initial oven temperature was 52°C (2 min). The amount of each fragrance volatile recovered (reported as ng / L of air) was determined using external standard calibration for each chemical. At least five acetone solutions were prepared with analyte concentrations ranging from 0.05 g / L to 5 g / L. The solutions were injected (0.2 μL) into Tenax® cartridges and desorbed as described above. Each solution was analyzed in triplicate. The calibration curve was passed through the origin.

[0143] Dynamic headspace concentrations (ng / L) of fragrance ingredients were obtained from line-dried cotton treated with fabric softeners containing enol ether fragrance precursors compared to their respective references (data from headspace samples at 60–75 min and 120–135 min).

[0144] [Table 1-1]

[0145] [Table 1-2] a. The headspace sampling cell was thermostated at 30°C.

[0146] 3. Olfactory evaluation using leave-on hair conditioner Model rinse-off hair conditioners were prepared by commonly known methods with the following compositions (wt %): Deionized water 95.50% Salcare SC 91 (Supplier: BASF) 1.00% Aculyn(TM) 46 (Supplier: Dow) 1.00% Wacker-Belsil® DMS 6038 (supplier: Wacker) 0.50% Phenonip(TM) (Supplied by Clariant) 0.50% Mirasil® ADM-E (supplier: Elkem) 1.50%

[0147] A 25% solution of the enol ether in isopropyl myristate or a 25% solution of the enol ether in acetone was dispersed in a leave-on hair conditioner to yield samples containing 0.15% or 0.25% by weight of the precursor, respectively. Reference samples containing equimolar levels of the potential ketone and formate were prepared in the same manner. The samples were allowed to acclimate at room temperature for one day. Hair swatches (10 g) were rinsed with warm tap water (37°C) for 30 seconds, and then the hair was gently combed and straightened. A sample of the hair conditioner (1 g) was applied to each swatch and massaged into the hair to ensure complete dispersion. The swatches were then hung to dry at room temperature. They were then olfactory evaluated by a panel for odor intensity after 6 and 24 hours. Panelists were asked to rate the perceived odor intensity on a scale ranging from 1 (not perceptible) to 7 (very strong). The data from the panel evaluation are summarized in the table below.

[0148] [Table 2]

[0149] These data show that the compounds of formula (I) produced a stronger odor intensity on hair than the corresponding reference samples both 6 and 24 hours after application from a leave-on hair conditioner, demonstrating that the compounds of the present invention produced the desired sustained release effect.

[0150] 4. Olfactory evaluation of rinse-off hair conditioners Model rinse-off hair conditioners were prepared by commonly known methods with the following compositions (wt %): Deionized water 92.54% Chlorhexidine dihydrochloride 0.05% Natrosol® 250 H (supplied by Hercules) 1.00% Dehyquart® C 4046 (Supplier: Cognis) 0.20% Mirasil® ADM-E (Supplier: Rhodia) 1.20% Genamin® KDM (Supplier: Clariant) 1.00% Crodamol® SS (Supplier: Croda) 0.50% Crodacol® C90 (Supplier: Croda) 3.01% Myristyl alcohol (supplied by Aldrich) 0.20% Nipagin® M (supplied by Nipa) 0.30%

[0151] A 25% solution of the enol ether in isopropyl myristate was dispersed in rinse-off hair conditioner to yield samples containing 0.25 wt. % or 0.15 wt. % precursor. Reference samples containing equimolar levels of the potential ketone and formate were prepared in the same manner. The samples were allowed to acclimate at room temperature for 1 day. Hair swatches (10 g) were wetted with warm tap water (37 °C) and washed with an unscented emulsion shampoo. Shampoo (1 mL) was dispensed along the length of each swatch using a syringe. The swatches were massaged with fingertips for 30 seconds to distribute the shampoo and create a good lather. They were then rinsed with warm tap water for 30 seconds and gently squeezed out of excess water. Rinse-off conditioner (1.0 g) was dispensed along the hair swatch and gently massaged into the hair for 1 minute. The swatches were then immersed in a 2 L beaker of warm tap water and moved up and down three times, then side to side three times. The hair was then rinsed under tap water for 30 seconds while detangling with fingertips. After gently squeezing out excess water, the swatches were hung to dry at room temperature. The swatches were then olfactory evaluated by a panel for odor intensity after 6 and 24 hours. Panelists were asked to rate the perceived odor intensity on a scale ranging from 1 (not perceptible) to 7 (very strong). The data from the panel evaluation are summarized in the table below.

[0152] [Table 3]

[0153] These data show that the compounds of formula (I) produced a stronger odor intensity on hair than the corresponding reference samples both 6 and 24 hours after application from a rinse-off hair conditioner, demonstrating that the compounds of the present invention produced the desired sustained release effect.

[0154] 5. Olfactory evaluation of pearlescent shampoo A model pearlescent shampoo was prepared in a commonly known manner with the following composition (% by weight): Deionized water 46.27% EDETA B POWDER (Supplier: BASF) 0.05% Jaguar C14 S® (supplied by Rhodia) 0.05% UCare(TM) Polymer JR-400 (Supplier: Dow) 0.075% 10%NaOH solution 0.30% Sulfetal LA BE (Supplier: Z&H Handel) 34.00% Zetesol LA® (supplied by Z&H Handel) 9.25% Tego® Betaine F 50 (Supplier: Evonik) 2.00% Xiameter® MEM-1691 (supplied by Dow Corning) 2.50% Cetyl Alcohol 1.20% Comperlan 100 (Supplied by: BTC Specialty Techn.) 1.50% Cutina® AGS (supplied by BASF) 2.00% Kathon(TM) CG (Supplied by: Dow) 0.10% Panthenol 75% (Supplier: BASF) 0.10% Sodium chloride 25% 0.60%

[0155] A 25% solution of the enol ether in isopropyl myristate was dispersed in pearlescent shampoo to yield a sample containing 0.15 wt% of the precursor. A reference sample containing equimolar levels of the potential ketone and formate ester was prepared in the same manner. The samples were allowed to acclimate at room temperature for one day. Hair swatches (10 g) were wetted with warm tap water (approximately 37°C) and washed with a milky shampoo. Shampoo (1 gram) was applied via syringe along the length of each swatch. The swatches were massaged with fingertips for 30 seconds to distribute the shampoo and create a good lather. They were then rinsed with warm tap water for 30 seconds and gently squeezed to remove excess water. The swatches were then washed again with pearlescent shampoo for 30 seconds and rinsed with warm tap water for 30 seconds. After gently squeezing out excess water, the swatches were hung to dry at room temperature. The swatches were then olfactory evaluated for odor intensity by a panel of 18-19 people after 6 and 24 hours. Panelists were asked to rate the perceived odor intensity on a scale ranging from 1 (not perceptible) to 7 (very strong). The data obtained from the panel evaluations are summarized in the table below.

[0156] [Table 4]

[0157] These data show that the compounds of formula (I) produced a stronger odor intensity on hair than the corresponding reference samples both 6 and 24 hours after application from the shampoo, demonstrating that the compounds of the present invention produced the desired sustained release effect.

[0158] 6. Olfactory evaluation using antiperspirant / deodorant sticks Model deodorants were prepared by commonly known methods with the following composition (wt%): Dow Corning 345 Fluid 55.00% Lanette® 18 (supplied by BASF) 21.00% Tegosoft® PBE (Supplier: Evonik) 2.00% Cutina® HR (supplied by BASF) 1.00% Summit(R) AZP-908 (Supplier: SummitReheis) 20.00%

[0159] Samples containing 0.15% by weight of an enol ether perfume precursor were prepared by dispersing a 15:20 mixture of enol ether and isopropyl myristate into a molten antiperspirant composition. Reference samples containing equimolar levels of the potential ketone and formate ester were prepared in the same manner. The molten samples were poured into deodorant stick molds and allowed to acclimate at room temperature for one day. A 0.25g amount of each sample was spread evenly on a 4.5cm x 12cm blotting paper. The blotting papers were stored under ambient conditions for 6 and 24 hours. The blotting papers were olfactory evaluated by a panel for odor intensity after 6 and 24 hours. Panelists were asked to rate the perceived odor intensity on a scale ranging from 1 (not perceptible) to 7 (very strong). The data obtained from the panel evaluations are summarized in the table below.

[0160] [Table 5]

[0161] These data show that compounds of formula (I) produced stronger odor intensity on blotter paper than the corresponding reference sample 6 hours after application from an antiperspirant stick, demonstrating that the compounds of the present invention produced the desired sustained release effect.

[0162] 7. Olfactory evaluation of eau de toilette A 1% solution of the enol ether in ethanol 40B and water (85:15 by weight) was prepared. Reference samples containing equimolar levels of the potential ketone and formate ester were prepared. If the mixtures were not homogeneous, both the enol ether and the corresponding reference sample were sonicated in a 25°C water bath for 10-20 minutes. 20 μl of each solution was applied to the center of a 4.5 cm x 12 cm blotter paper. The blotter paper was stored under ambient conditions for 3 and 6 hours. The blotter paper was olfactory evaluated for odor intensity after 6 and 24 hours by a panel of 20-25 people. Panelists were asked to rate the perceived odor intensity on a scale ranging from 1 (not perceptible) to 7 (very strong). The data obtained from the panel evaluation are summarized in the table below.

[0163] [Table 6]

[0164] These data show that compounds of formula (I) produced stronger odor intensities on blotter paper than the corresponding reference samples 3 and 6 hours after application from ethanolic solution, demonstrating that the compounds of the present invention produced the desired sustained release effect.

[0165] 8. Performance of the Compounds of the Present Invention and the Compounds (Comparative Examples) Disclosed in U.S. Patent Publication No. 3004 / 0013779 in Fabric Softener Applications To compare the performance of these enol ethers as perfume precursors, fabric softener samples were prepared as described above by mixing 0.075 mmol of Enol Ether Example 1 with 0.075 mmol of one of the enol ether compounds disclosed in U.S. Patent Application Publication No. 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 U.S. Patent Application Publication No. 2004 / 0013779 using dodecenal and 1-butanol as starting materials and isolated as a mixture of isomers (E / Z = 44:56). Cotton swatches were rinsed with the fabric softener samples as described above, hung to dry (15-16 hours), and then subjected to dynamic headspace analysis. The table below summarizes the average headspace concentrations measured for the released carbonyl compounds (2-undecanone or undecanal). In each case, the headspace concentrations of 2-undecanone released by Example 1 were significantly higher than the concentrations 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 either of the enol ethers disclosed in U.S. Patent Application Publication No. 2004 / 0013779. In the 60-75 minute headspace samples, Example 1 released 14-fold and 3.3-fold higher concentrations of 2-undecanone compared to the levels of undecanal released by 1-ethoxydodec-1-ene or 1-butoxydodec-1-ene, respectively.

[0166] The dynamic headspace concentrations (ng / L) of perfume raw materials obtained from line-dried cotton treated with fabric softeners containing Example 1 and either 1-ethoxydodec-1-ene or 1-butoxydodec-1-ene (data for 60-75 minute and 120-135 minute headspace samples and standard deviations) are summarized in the table below.

[0167] [Table 7]

[0168] 9. Hydrolysis Rates of the Compounds of the Present Invention and the Compounds (Comparative Examples) Disclosed in U.S. Patent Application Publication No. 3004 / 0013779 The hydrolysis rates of 1-ethoxydodec-1-ene and 1-butoxydodec-1-ene of Example 1 under acidic conditions were determined as predictors of stability in acidic consumer products (Figure 1). Susceptibility to acid-catalyzed hydrolysis results in loss of the enol ether, thereby limiting long-term storage stability. Each enol ether was dissolved in a 4:1 mixture of THF / 0.1M HCl, and the percent remaining over time relative to an internal standard was determined according to the following procedure.

[0169] In a 15 mL vial, 125 mg of the enol ether, 60 mg of hexadecane, and 10 mL of THF (purged with N2 and containing 2500 ppm BHT) were added. After mixing, 2 mL of this solution was removed with a volumetric pipette and used to obtain a time-zero measurement. 2 mL of 0.1 M HCl was mixed with the remaining 8 mL of THF solution. This mixture was divided into 5 mL vials (1 mL per vial). Argon was gently introduced into the top of the vial, and a screw cap was attached and wrapped around it with parafilm. The vials were stored at room temperature until analysis. For analysis, 2 mL of ethyl acetate was added to the vial and mixed. After phase separation, the upper phase was collected and washed with saturated sodium carbonate (1 mL). Samples of the organic phase were analyzed in duplicate by GC-FID. For the time-zero sample, 0.5 mL of deionized water was added to 2 mL of the original THF solution. One mL of this solution was placed in 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 remaining enol ether was determined by comparing the ratio of the integrated peak areas of the analyte and the internal standard to the ratio measured at time zero.

[0170] Figure 1 below shows that both 1-ethoxydodec-1-ene and 1-butoxydodec-1-ene hydrolyzed much faster than Example 1. After 6 days, only 3% and 8.8% of 1-ethoxydodec-1-ene and 1-butoxydodec-1-ene remained, while 83% of Example 1 remained intact. Therefore, the enol ethers described in U.S. Patent Application Publication No. 2004 / 00137791 are predicted to be less stable in acidic consumer products, such as fabric softeners. This higher susceptibility to hydrolysis, and the resulting lower stability, is overcome by the enol ethers of the present invention because they have a much slower hydrolysis rate.

[0171] 10. Preparation of liquid detergents containing the compounds of the present invention [Table 8] 1)Hostapur SAS 60;Supplier:Clariant 2)Edenor K 12-18;Supplier:Cognis 3) Genapol LA 070;Supplier: Clariant 4)Supplier: Genencor International 5)Aculyn 88;Supplier:Dow Chemical

[0172] Liquid detergents are prepared by adding 0.005 to 5% by weight of one or more compounds of Examples 1 to 29, based on the total weight of the liquid detergent, to the unscented liquid detergent formulation of Table 1 with gentle shaking.

[0173] 11. Preparation of a clear, homogeneous shampoo formulation containing a compound of the present invention [Table 9] 1) Ucare Polymer JR-400, supplier: Noveon 2) Supplier: Schweizerhall 3) Glydant, Supplied by: Lonza 4) Texapon NSO IS, Supplier: Cognis 5) Tego Betain F 50, supplier: Evonik 6) Amphotensid GB 2009, supplier: Zschimmer & Schwarz 7) Monomuls 90 L-12, supplier: Gruenau 8) Nipagin Monosodium, Supplier: NIPA

[0174] The shampoo is prepared by dispersing Polyquaternium-10 in water. The remaining ingredients of Phase A are mixed separately by adding them in order, mixing well after each addition. This premix is ​​added to the Polyquaternium-10 dispersion and mixed for an additional 5 minutes. Then, with stirring, premixed Phase B and premixed Phase C are added (Monomuls 90L-12 heated to melt in Texapon NSO IS). Phases D and E are added with stirring. The pH is adjusted with citric acid solution until the pH is 5.5-6.0 to obtain the fragrance-free shampoo formulation.

[0175] Perfumed shampoos were prepared by adding 0.005 to 5% by weight of one or more compounds of Examples 1 to 29, based on the total weight of the shampoo, to the unscented shampoo formulation of Table 2 with gentle shaking.

[0176] 12. Preparation of structured shower gels containing the compositions of the present invention [Table 10] 1) EDETA B POWDER; Trademark and Supplier: BASF 2) CARBOPOL AQUA SF-1 POLYMER; Trademark and Supplier: NOVEON 3) ZETESOL AO 328 U; Trademark and Supplier: ZSCHIMMER & SCHWARZ 4) TEGO-BETAIN F 50; Trademark and Supplier: GOLDSCHMIDT 5) KATHON CG; Trademark and Supplier: ROHM & HASS

[0177] Shower gels are prepared by adding 0.005 to 5% by weight of one or more compounds of Examples 1 to 29, based on the total weight of the shower gel, to the unscented shower gel formulation of Table 3, with gentle shaking.

[0178] 13. Preparation of a clear shower gel containing the composition of the present invention [Table 11] 1) EDETA B POWDER; Trademark and Supplier: BASF 2) ZETESOL AO 328 U; Trademark and Supplier: ZSCHIMMER & SCHWARZ 3) TEGO-BETAIN F 50; Trademark and Supplier: GOLDSCHMIDT 4) MERQUAT 550; Trademark and Supplier: LUBRIZOL

[0179] Clear shower gels are prepared by adding 0.005 to 5% by weight of one or more compounds of Examples 1 to 29, based on the total weight of the shower gel, to the unscented shower gel formulation of Table 4, while shaking gently.

[0180] 14. Preparation of a milky shower gel containing the composition of the present invention [Table 12] 1) EDETA B POWDER; Trademark and Supplier: BASF 2) Texapon NSO IS; Trademark and Supplier: COGNIS 3) MERQUAT 550; Trademark and Supplier: LUBRIZOL 4) DEHYTON AB-30; Trademark and Supplier: COGNIS 5) GLUCAMATE LT; Trademark and Supplier: LUBRIZOL 6) EUPERLAN PK 3000 AM; Trademark and Supplier: COGNIS 7) CREMOPHOR RH 40; Trademark and Supplier: BASF

[0181] Clear shower gels are prepared by adding 0.005 to 5% by weight of one or more compounds of Examples 1 to 29, based on the total weight of the shower gel, to the unscented shower gel formulation of Table 5, while shaking gently.

Claims

1. Compounds of formula (I) 【Chemistry 1】 [In the formula, R １ is C １～８ Alkyl, C １～８ Alkoxy, hydroxy, carboxylic acid, and / or C １～４ C, each optionally substituted with one or more carboxylic acid ester groups １～１５ Alkyl, C １～１５ Alkoxy, C ３～１５ Cycloalkyl, C ５～１５ Cycloalkenyl, C ６～１０ aryl, and / or C ６～１０ C, each optionally substituted with one or more aryloxy groups １～１５ Alkyl, C ２～１５ Alkenyl, C ３～１５ Cycloalkyl, C ５～１５ cycloalkenyl, or C ６～１０ represents an aryl group; R ２ is C １～１５ represents an alkyl group; R １ and R ２ When these are taken together, C １～８ Alkyl, C １～８ Alkoxy, carboxylic acid, 4-methylcyclohex-3-en-1-yl, and / or C １～４ C, each optionally substituted with one or more carboxylic acid ester groups 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 C, each optionally substituted with one or more aryloxy groups ５～１５ Cycloalkyl, C ５～１５ Cycloalkenyl, C ４～１４ heterocycloalkyl, or C ４～１４ forming heterocycloalkenyl groups, wherein said heteroatoms represent one or more oxygens; R ４ are each independently hydrogen or C １～５ represents an alkyl group; R １ and R ４ When these are taken together, C １～８ Alkyl, C １～８ Alkoxy, carboxylic acid, and / or C １～４ C, each optionally substituted with one or more carboxylic acid ester groups １～１５ Alkyl, C １～１５ Alkoxy, C ３～１５ Cycloalkyl, C ５～１５ Cycloalkenyl, C ６～１０ aryl, and / or C ６～１０ C, each optionally substituted with one or more aryloxy groups ３～１５ Cycloalkyl or C ５～１５ forming a cycloalkenyl group, R ３ represents hydrogen or C １～８ Alkyl, C １～８ Alkoxy, carboxylic acid, and / or C １～４ C, each optionally substituted with one or more carboxylic acid ester groups １～１５ Alkyl, C １～１５ Alkoxy, C ３～１５ Cycloalkyl, C ５～１５ Cycloalkenyl, C ６～１０ aryl, and / or C ６～１０ C, each optionally substituted with one or more aryloxy groups １～１５ Alkyl, C ２～１５ Alkenyl, C ３～１５ cycloalkyl, or C ５～１５ represents a cycloalkenyl group; R ３ and R ４ When these are taken together, C １～８ Alkyl, C １～８ Alkoxy, carboxylic acid, and / or C １～４ C, each optionally substituted with one or more carboxylic acid ester groups １～１５ Alkyl, C １～１５ Alkoxy, C ３～１５ Cycloalkyl, C ５～１５ Cycloalkenyl, C ６～１０ aryl, and / or C ６～１０ C, each optionally substituted with one or more aryloxy groups ３～１５ Cycloalkyl or C ５～１５ forming a cycloalkenyl group] 2. Use of a compound of formula (I) as a perfuming ingredient to impart a long-lasting odor to an environment in which is oxidized.

2. A method for imparting, enhancing, improving or modifying the olfactory characteristics of a perfumed composition, the air surrounding the perfumed composition, a surface, or a perfumed article, comprising adding to the composition, air, or article an effective amount of at least one compound of formula (I) as defined in claim 1, or contacting or treating a surface with an effective amount of at least one compound of formula (I) as defined in claim 1.

3. at least one active ketone of formula (II) on the surface or in the air surrounding the perfuming composition 【Chemistry 2】 [In the formula, R １ , R ２ , and R ４ have the same meaning as defined in claim 1], At least one activated formate ester of formula (III) 【Transformation 3】 [In the formula, R ３ , and R ４ have the same meaning as defined in claim 1], and / or at least one activated alcohol of formula (IV) 【Chemistry 4】 [In the formula, R ３ and R ４ have the same meaning as defined in claim 1.

1. A method for enhancing or prolonging the diffusion effect of a characteristic fragrance of a surface or the air, wherein the surface or the air is treated with at least one compound (I) as defined in claim 1 or with a composition or article containing at least one compound (I) under conditions that allow the release over time of at least one active ketone of formula (II), at least one active formate ester of formula (III), and / or at least one active alcohol of formula (IV).

4. i) at least one compound of formula (I) as defined in claim 1; ii) at least one ingredient selected from the group consisting of a perfume carrier and a perfume base; and iii) optionally at least one perfume adjuvant; A fragrance composition comprising:

5. A perfumed consumer product containing at least one compound of formula (I) as defined in claim 1 or a perfume composition as defined in claim 4.

6. 6. The perfumed consumer product of claim 5, wherein the perfumed consumer product is a perfume, a fabric care product, a body care product, a cosmetic, a skin care product, an air care product, or a home care product.

7. 7. The perfumed consumer product of claim 6, characterized in that it is a fine perfume, splash or eau de parfum, cologne, shave or aftershave lotion, liquid or solid detergent, fabric softener, fabric refresher, ironing water, paper, bleach, carpet cleaner, curtain care product, shampoo, coloring preparation, color care product, hair styling product, dental care product, disinfectant, intimate care product, hairspray, hair conditioning product, vanishing cream, deodorant or antiperspirant, depilatory, tanning agent or sunscreen, nail product, skin cleanser, cosmetic, scented soap, shower or bath mousse, oil or gel, or foot / hand care product, hygiene product, deodorizer, "ready to use" powder air freshener, mold remover, furniture care product, wipe, dish detergent or hard surface cleaner, leather care product, car care product.

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