Musk odorant

Abstract

The present invention relates to the field of perfumery. More specifically, the present invention relates to the compounds of formula (I) defined in the present invention and their use as perfuming ingredients. Thus, as mentioned herein, the present invention also includes the compounds of the present invention as part of perfuming compositions or perfuming consumer products.

Description

[Technical field]

[0001] The present invention relates to the field of perfumery. More specifically, the present invention relates to a compound of formula (I) as defined below, and its use as a perfuming ingredient. Thus, as referred to hereinafter, the present invention also includes the compound of the present invention as part of a perfuming composition or a perfuming consumer product.

[0002] Background technology Ingredients that impart musk notes are highly valued and widely used in the perfume industry, as they are considered one of the important base notes of perfumes. Since the 1990s, the discovery of Helvetolide® (trademark of Firmenich SA, Suisse), reported in EP 0472966, has increased interest in this family of alicyclic compounds that fuse musk notes with fruity and amber notes. In the prior art, 3,3-dimethylcyclopentyl analogues are described as weak and lacking in persistence. In US 2006046955, unsaturated 6-membered ring analogues are reported. However, these compounds, especially 2-[1-(3,3-dimethyl-1-cyclohexen-1-yl)ethoxy]-2-methylpropylpropanoate, were less effective than Helvetolide®.

[0003] Thus, there remains a need to develop alicyclic musk compounds that impart a strong and substantial musk note.

[0004] The present invention provides a novel alicyclic perfume ingredient of formula (I) containing a hitherto unreported unsaturated 5-membered ring, which imparts a musk note while maintaining good substantivity similar to that of Helvetolide®. The above-mentioned prior art documents do not disclose the compound of formula (I) or the sensory properties of the compound of formula (I).

[0005] Description of the invention Surprisingly, it has been found that compounds of formula (I) exhibit a musk note which is particularly appreciated in perfumery.

[0006] A first object of the present invention is to provide a compound of formula (I) [ka] [wherein one dotted line represents a carbon-carbon double bond and the other dotted line represents a carbon-carbon single bond; n is 0 or 1; X is C(=O) or C(Me) 2 R is a hydrogen atom, C 1-6 Alkyl group, C 1-6 Alkoxy group, C 2-6 Alkenyl group, C 2-6 Alkynyl group or C 3-6 Cycloalkyl groups, C(=O)R' or CH(OR'')R'' groups, where R' is C 1-3 Alkyl group or C 1-3 alkoxyl group, and R″ is independently a hydrogen atom or C 1-3 is an alkyl group), in the form of any one of its stereoisomers or a mixture thereof.

[0007] Said compounds can be used as perfuming ingredients, for example to impart musk-type odor notes with red fruit aspects.

[0008] For reasons of clarity, with regard to the expression "any one of its stereoisomers or a mixture thereof" or similar expressions, the usual meaning understood by a person skilled in the art is meant, i.e. that the compound of formula (I) may be a pure enantiomer or a diastereomer. In other words, the compound of formula (I) may have several stereocenters, each of which may have two different stereochemistries (e.g. R or S). The compound of formula (I) may be in the form of a pure enantiomer or even in the form of a mixture of enantiomers or diastereomers. The compound of formula (I) may be in racemic or scalemic form. Thus, the compound of formula (I) may be in the form of a stereoisomer or a composition of matter that comprises or consists of various stereoisomers.

[0009] For reasons of clarity, with regard to the expression "one dotted line represents a carbon-carbon double bond and the other dotted line represents a carbon-carbon single bond" or similar expressions, it means the usual meaning understood by a person skilled in the art, i.e., that the entire bond (solid and dotted) between the carbon atoms connected by the dotted line is a carbon-carbon single or double bond. In other words, when the compound of formula (I) contains a cyclopentyl group and has the formula [ka] wherein X, n and R have the same meanings as defined above, in the form of any one of its stereoisomers or a mixture thereof.

[0010] According to any embodiment of the present invention, the compound of the present invention may be in the form of a composition comprising a compound of formula (Ia) and a compound of formula (Ib). More specifically, the composition may comprise 20-90% (w / w) of the compound of formula (Ia) and 5-50% (w / w) of the compound of formula (Ib), the percentages being relative to the total weight of the composition.

[0011] The terms "alkyl", "alkoxyl", "alkenyl" and "alkynyl" are understood to include branched and straight chain alkyl, alkoxyl, alkenyl and alkynyl groups. The term "alkynyl" is understood to include one olefinic double bond. The term "alkynyl" is understood to include one triple bond. The term "cycloalkyl" is understood to include monocyclic groups.

[0012] According to any one of the above embodiments of the present invention, the compound (I) is 12 ~C 20 Compounds, preferably C 14 ~C 27 It is.

[0013] According to a particular embodiment, X is C=(O) where n is 0.

[0014] According to a particular embodiment, when n is 0, R is C 1-6 Alkoxy groups, especially C 1-3 Alkoxy groups, especially C 1-2 It may be an alkoxyl group, and more specifically an ethoxyl group.

[0015] According to any one of the above embodiments of the invention, n may be 1.

[0016] According to any one of the above embodiments of the invention, X is C(Me) 2 It may be a group.

[0017] According to any one of the above embodiments of the invention, the compound of formula (I) may be represented by the formula (II) [ka] wherein the dotted line and R have the same meaning as defined above, in the form of any one of its stereoisomers or a mixture thereof.

[0018] According to any one of the above embodiments of the invention, R is a hydrogen atom, C1-4 Alkyl group, C 1-4 Alkoxy group, C 2-4 Alkenyl group, C 2-4 Alkynyl group or C 3-6 Cycloalkyl groups, C(=O)R' or CH(OR'')R'' groups, where R' is C 1-3 Alkyl group or C 1-3 alkoxyl group, and R″ is independently a hydrogen atom or C 1-3 In particular, R may be a hydrogen atom, C 1-3 Alkyl group, C 1-3 Alkoxy group, C 2-3 Alkenyl group, C 2-3 Alkynyl group or C 3-6 Cycloalkyl groups, C(=O)R' or CH(OR'')R'' groups, where R' is C 1-2 Alkyl group or C 1-2 alkoxyl group, and R″ is independently a hydrogen atom or C 1-2 In particular, R may be a hydrogen atom, C 1-3 Alkyl group, C 1-3 Alkoxy group, C 2-3 Alkenyl group, C 2-3 Alkynyl group or C 3-6 Cycloalkyl groups, CH(OH)Me groups, CH 2 OH group or C(=O)R' group (where R' is C 1-2 Alkyl group or C 1-2 In particular, R may be C 1-3 Alkyl group, C 1-3 Alkoxy group, C 2-3 Alkenyl group, C 2-3 Alkynyl group or C 3 Cycloalkyl groups, or C(=O)R' groups, where R' is C 1-2 In particular, R may be an ethyl, propyl, ethoxy, prop-1-en-1-yl, 2-ethynyl or cyclopropyl group, or a C(=O)Me group. In particular, R may be an ethyl, propyl or prop-1-en-1-yl group. Even more particularly, R may be an ethyl group.

[0019] According to any one of the above embodiments of the invention, the compound of formula (I) may be represented by the formula (III) [ka] in the form of any one of its isomers or a mixture thereof.

[0020] As a specific example of the compound of the present invention, a non-limiting example may be mentioned, which comprises 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropionate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropionate in a ratio of 80:20, imparting a red fruit note, in particular a musk note associated with raspberry. The composition of the present invention also exhibits the cooked apple note of delta damascene. The composition of the present invention exhibits strong top and heart notes while maintaining a high persistence comparable to Helvetolide®.

[0021] Another example may be 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropionate, which has a similar odor as above.

[0022] As examples of compounds of the invention without any other specific limitations, mention may be made of those in the following Table 1.

[0023] [Table 1-1] [Table 1-2] [Table 1-3] [Table 1-4]

[0024] For reasons of clarity, the wavy bonds in the compositions of matter containing the compounds in the above table, i.e. 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butenoate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butenoate, or similar, have the usual meaning as understood by a person skilled in the art, i.e. the double bonds may have a cis configuration corresponding to the Z isomer, a trans configuration corresponding to the E isomer, or a mixture thereof. In other words, the compounds may be in the form of E or Z isomers, or a mixture thereof, for example, the method of the present invention results in a composition consisting of one or more of the compounds having the same chemical structure but different configurations of the double bonds.

[0025] The compounds of the present invention are surprisingly very potent. All the comparative compounds listed below are structurally close to the compounds of the present invention and impart less interesting and weaker odor notes. Only the compounds of the present invention impart a strong and substantial odor.

[0026] According to a particular embodiment of the invention, the compound of formula (I) is 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropionate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropionate or a mixture thereof; 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-oxoethylpropionate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-oxoethylpropionate. pionate or mixtures thereof;2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl cyclopropanecarboxylate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl cyclopropanecarboxylate or mixtures thereof;1-(3,3-dimethyl-1-cyclopenten-1-yl)ethyl ethylmalonate, 1-(4,4-dimethyl-1-cyclopenten-1-yl)ethyl ethylmalonate or mixtures thereof;2-[1-( 3,3-Dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butanoate, 2-[1-(4,4-Dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butanoate or mixtures thereof; 2-[1-(3,3-Dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-hydroxypropanoate, 2-[1-(4,4-Dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-hydroxypropanoate or mixtures thereof 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl ethyl carbonate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl ethyl carbonate or mixtures thereof; 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl methoxy acetate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl methoxy acetate or mixtures thereof;2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-oxopropanoate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-oxopropanoate or mixtures thereof; 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl ethyl oxalate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl ethyl oxalate or mixtures thereof; 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl propiolate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl propiolate or 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butynoate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butynoate or mixtures thereof; 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl acrylate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl acrylate or mixtures thereof; 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl butyrate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl butyrate or mixtures thereof. In particular, the compound of formula (I) is 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl propionate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl propionate or mixtures thereof; 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl cyclopropane carboxylate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl cyclopropane carboxylate or mixtures thereof;1-(3,3-dimethyl-1-cyclopenten-1-yl)ethyl ethyl malonate, 1-(4,4-dimethyl-1-cyclopenten-1-yl)ethyl ethyl malonate or mixtures thereof;2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butanoate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butanoate or mixtures thereof;2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl ethyl carbonate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl ethyl carbonate or mixtures thereof;2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl ethyl carbonate 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-oxopropanoate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-oxopropanoate or mixtures thereof; 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl propiolate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl propiolate or mixtures thereof; 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl butyrate, 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl butyrate or mixtures thereof. More specifically, the compound of formula (I) is a composition comprising 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl propionate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl propionate;

[0027] When comparing the note of the compounds of the present invention with that of the prior art compound 2-[1-(3,3-dimethyl-1-cyclohexen-1-yl)ethoxy]-2-methylpropylpropanoate, the compounds of the present invention are distinguished by their lack of the apparently strong musky note associated with raspberry notes and the powdery note characteristic of the prior art compounds.Furthermore, the compounds of the present invention impart a noticeably stronger and more substantial note similar to Helvetolide®.

[0028] The odour of the compounds of the invention is also distinguished from those of the prior art by the absence or noticing of the animal and ambrette notes characteristic of the prior art compounds, which differences make the compounds according to the invention and the prior art compounds respectively suitable for different uses, i.e. giving different organoleptic impressions.

[0029] As mentioned above, the present invention relates to the use of a compound of formula (I) as a perfuming ingredient. In other words, the present invention relates to a method for imparting, enhancing, improving or modifying the odor characteristics of a perfuming composition or a perfumed article or surface, which method comprises adding to said composition or article at least an effective amount of a compound of formula (I), for example imparting its typical note. It is understood that the final pleasant effect may depend on the exact dosage and organoleptic properties of the compound of the present invention, but in any case, the addition of the compound of the present invention imparts to the final product its typical touch in the form of a note, touch or aspect, depending on the dosage.

[0030] With regard to "use of a compound of formula (I)", the use of any composition which comprises a compound of formula (I) and which may be advantageously used in the perfumery industry is to be understood here.

[0031] Said composition, which is in fact advantageously used as a perfuming ingredient, is also an object of the present invention.

[0032] Therefore, another object of the present invention is to i) as perfuming ingredient, at least one compound of the invention as defined above, ii) at least one ingredient selected from the group consisting of a perfume carrier and a perfume base; and iii) optionally at least one flavouring adjuvant; A fragrance composition comprising:

[0033] By "perfume carrier" is meant herein a material that is practically neutral from the perfume point of view, i.e. does not significantly modify the organoleptic properties of the perfuming ingredients. Said carrier may be liquid or solid.

[0034] The liquid carrier may include, but is not limited to, emulsifying systems, i.e., solvent and surfactant systems, or solvents commonly used in perfumery.A detailed description of the nature and type of solvents commonly used in perfumery cannot be exhaustive.However, it includes, but is not limited to, the most commonly used 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, Abalyn® (rosin resin, available from Eastman), benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethanol, triethyl citrate, or mixtures thereof, or naturally occurring solvents, such as glycerol, or vegetable oils, such as palm oil, sunflower oil or linseed oil. With regard to compositions comprising both a fragrance carrier and a fragrance base, other fragrance carriers which may be suitable than those mentioned above may be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trade name Isopar® (supplier: Exxon Chemical) or glycol ethers and glycol ether esters such as those known under the trade name Dowanol® (supplier: Dow Chemical Company), or hydrogenated castor oil such as those known under the trade name Cremophor® RH 40 (supplier: BASF).

[0035] Solid carrier is meant to denote a material capable of chemically or physically binding the perfume composition or some of its components. Generally, such solid carriers are used to stabilize the composition or to adjust the rate of evaporation of the composition or some of its components. Solid carriers are currently used in the art, and the skilled artisan knows how to achieve the desired effect. However, as non-limiting examples of solid carriers, mention may be made of absorbent gums or polymers or inorganic materials, such as porous polymers, cyclodextrins, dextrins, maltodextrins, wood materials, organic or inorganic gels, clays, gypsum talc or zeolites.

[0036] Other non-limiting examples of solid carriers may include encapsulating materials. Examples of such materials include wall forming and plasticizing materials such as glucose syrup, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, proteins or pectins, vegetable gums such as gum acacia (gum arabic), urea, sodium chloride, sodium sulfate, zeolites, sodium carbonate, sodium bicarbonate, clays, talc, calcium carbonate, magnesium sulfate, gypsum, calcium sulfate, magnesium oxide, zinc oxide, titanium dioxide, calcium chloride, potassium chloride, magnesium chloride, zinc chloride, carbohydrates, sugars such as sucrose, monosaccharides, disaccharides, and polysaccharides and derivatives such as chitosan, starch, cellulose, carboxymethyl methylcellulose, ... cellulose, hydroxyethylcellulose, ethylcellulose, propylcellulose, polyols / sugar alcohols such as sorbitol, maltitol, xylitol, erythritol, isomalt, polyethylene glycol (PEG), polyvinylpyrrolidine (PVP), polyvinyl alcohol, acrylamides, acrylates, polyacrylic acid and related, maleic anhydride copolymers, amine functional polymers, vinyl ethers, styrene, polystyrene sulfonates, vinyl acids, ethylene glycol-propylene glycol block copolymers, vegetable gums, acacia gum, pectin, xanthan, alginates, carrageenan, citric acid or water soluble solid acids, fatty alcohols or fatty acids and mixtures thereof, Or it may comprise materials cited in references 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 method well known to those skilled in the art and may be carried out by using techniques such as spray drying, coagulation or even extrusion, or may consist of coat encapsulation, including coacervation and complex coacervation techniques.

[0037] Non-limiting examples of solid carriers may include core-shell capsules with aminoplast, polyamide, polyester, polyurea or polyurethane type resins or mixtures thereof (all of the aforementioned resins are well known to those skilled in the art) using techniques such as phase separation processes induced by polymerization, by interfacial polymerization, by coacervation, or all of the aforementioned techniques (all of the aforementioned techniques are described in the prior art), optionally in the presence of polymeric stabilizers or cationic copolymers.

[0038] The resins may be prepared by polycondensation of aldehydes (e.g., formaldehyde, 2,2-dimethoxyethanol, glyoxal, glyoxylic acid or glycolaldehyde and mixtures thereof) with amines, such as urea, benzoguanamine, glycouril, melamine, methylolmelamine, methylated methylolmelamine, guanazole, etc., and mixtures thereof. Alternatively, preformed resins, alkylated polyamines, such as those commercially available under the trade names Urac® (supplied by Cytec Technology Corp.), Cymel® (supplied by Cytec Technology Corp.), Urecoll® or Luracoll® (supplied by BASF) may be used.

[0039] Other resins are preferably prepared by polycondensation of a polyol, such as glycerol, and a polyisocyanate, such as the trimer of hexamethylene diisocyanate, the trimer of isophorone diisocyanate, or xylylene diisocyanate, or the biuret of hexamethylene diisocyanate, or the trimer of xylylene diisocyanate with trimethylolpropane (known under the trade name Takenate®, supplier: Mitsui Chemicals), preferably the trimer of xylylene diisocyanate with trimethylolpropane and the biuret of hexamethylene diisocyanate.

[0040] Some of the productive literature on the encapsulation of perfumes by polycondensation of amino resins, i.e. melamine-based resins, with aldehydes includes those published in Acta Polymerica by K. Dietrich et al. (Acta Polymerica, 1989, vol. 40, pages 243, 325 and 683, as well as 1990, vol. 41, page 91). Such literature already describes the various parameters that affect the production of such core-shell microcapsules, according to the prior art methods that are explained in more detail and exemplified in the patent literature. US 4'396'670 (Wiggins Teape Group Limited) is a good early example of such literature. Since then, many other authors have enriched the literature in this field, and while it is not possible to cover here all the developments that have been published, a general knowledge of encapsulation techniques is very important. Representative recent relevant literature disclosing suitable uses of such microcapsules is, for example, provided by K. Bruyninckx and M. Dusselier (ACS Sustainable Chemistry & Engineering, 2019, vol. 7, pages 8041-8054).

[0041] By "perfume base" is meant herein a composition comprising at least one perfuming co-ingredient.

[0042] Said perfuming co-ingredient is not of formula (I).Furthermore, by "perfuming co-ingredient", it is meant herein a compound that is used in perfuming preparations or compositions to provide a pleasant effect, i.e., is used mainly for the purpose of providing or adjusting odor.In other words, such co-ingredients to be considered as perfuming co-ingredients must be recognized by those skilled in the art as being capable of providing or modifying the odor of the composition in a positive or favorable way, and not simply having one odor.Perfuming components may provide additional benefits other than modifying or providing odor, such as persistence, blooming, malodor neutralization, antibacterial effect, antiviral effect, microbial stability, or pest control.

[0043] The nature and type of perfuming co-ingredients present in said base, which in any case will not be exhaustive, do not warrant a more detailed description here, whereby a person skilled in the art can select said base on the basis of his general knowledge and according to any use or application and the organoleptic effect desired. In general terms, these perfuming co-ingredients belong to various chemical classes: alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen or sulfur heterocyclic compounds and essential oils, and said perfuming co-ingredients may be of natural or synthetic origin.

[0044] Mention may in particular be made of the perfuming co-ingredients customarily used in perfume formulations, such as: - aldehyde components: decanal, dodecanal, 2-methyl-undecanal, 10-undecanal, octanal, nonanal and / or nonenal; - Aromatic Herbal Ingredients: Eucalyptus Oil, Camphor, Eucalyptol, 5-Methyltricyclo[6.2.1.0 2,7]undecane-4-one, 1-methoxy-3-hexanethiol, 2-ethyl-4,4-dimethyl-1,3-oxathiane, 2,2,7 / 8,9 / 10-tetramethylspiro[5.5]undec-8-en-1-one, menthol and / or alpha-pinene; - Balsam components: coumarin, ethyl vanillin and / or vanillin; - citrus constituents, dihydromyricenol, 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, (1E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1-penten-3-one, 1-(2,6,6-trimethyl-1,3-cyclohexadien-1-yl)-2-buten-1-one, (2E)-1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, (2E)-1-[2,6,6-trimethyl-3-cyclohexen-1-yl]-2-buten-1-one, (2E)-1-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2- Buten-1-one, 2,5-dimethyl-2-indanmethanol, 2,6,6-trimethyl-3-cyclohexene-1-carboxylate, 3-(4,4-dimethyl-1-cyclohexen-1-yl)propanal, 3-(3,3 / 1,1-dimethyl-5-indanyl)propanal, hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, vergyl acetate, geraniol, p-mentha-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, virgyl propionate, geranyl acetate, tetrahydrolinalool, cis-7-p-methanol, 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, amylcinnamaldehyde, 8-decen-5-olide, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, vergyl isobutyrate and / or a mixture of methyl ionone isomers; - fruity ingredients: gamma-undecalactone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-methyl-4-propyl-1,3-oxathiane, 4-decanolide, ethyl 2-methyl-pentanoate, hexyl acetate, ethyl 2-methylbutanoate, gamma-nonalactone, allylheptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-acetate, diethyl 1,4-cyclohexanedicarboxylate, 3-methyl-2-hexen-1-yl acetate, 1-[3,3-dimethylcyclohexyl]ethyl[3-ethyl-2-oxiranyl]acetate and / or diethyl 1,4-cyclohexanedicarboxylate; - green ingredients: 2-methyl-3-hexanone (E)-oxime, 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, (Z)-4-cyclopentadecen-1-one, 3-methylcyclopentadecanone, 1-oxa-12-cyclohexadecen-2-one, 1-oxa-13-cyclohexadecen-2-one, (9Z)-9-cycloheptadecen-1-one, 2-{(1S)-1-[(1R)-3,3-dimethylcyclohexyl]ethoxy}-2-oxaethylpropionate, 3-methyl-5-cyclo lopentadecen-1-one, 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopenta[g]isochromene, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropylpropanoate, oxacyclohexadecan-2-one and / or (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methylpropanoate; - Woody ingredients: 1-[(1RS,6SR)-2,2,6-trimethylcyclohexyl]-3-hexanol, 3,3-dimethyl-5-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-4-penten-2-ol, 3,4'-dimethylspiro[oxirane-2,9'-tricyclo[6.2.1.02,7]undec[4]ene, (1-ethoxyethoxy)cyclododecane, 2,2,9,11-tetramethylspiro[5.5]undec-8-en-1-yl acetate, 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-1-ethanone, patchouli oil, terpene fraction of patchouli oil, clearwood® (source: Firmenich SA), (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 of its stereoisomers, heliotropin, anisaldehyde, eugenol, cinnamaldehyde, clove oil, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal, 7-methyl-2H-1,5-benzodioxepin-3(4H)-one, 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydro-2-naphthalenol, 1-phenylvinyl acetate, 6-methyl-7-oxa-1-thia-4-azaspiro[4.4]nonane and / or 3-(3-isopropyl-1-phenyl)butanal.

[0045] The perfume base according to the invention may be, but is not limited to, the perfuming co-ingredients mentioned above, many others of which are in any case mentioned in references, for example in Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, by S. Arctander, or in its latest editions, or in other works of a similar nature, as well as in the abundant patent literature in the field of perfumery. It is also understood that said co-ingredients may be compounds known to release various types of perfuming compounds in a controlled manner, also known as properfumes or profragrances. Non-limiting examples of suitable pro-fragrances include 4-(dodecylthio)-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-butanone, 4-(dodecylthio)-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butanone, trans-3-(dodecylthio)-1-(2,6,6-trimethyl-3-cyclohexen-1-yl)-1-butanone, 3-(dodecylsulfonyl)-1-(2,6,6-trimethylcyclohex-3-en-1-yl)butan-1-one, linear polysiloxane copolymers of (3-mercaptopropyl)(methyl)dimethoxysilane, 2-(dodecylthio)octane-1-one ... 4-one, 2-(dodecylsulfonyl)octan-4-one, 4-oxooctane-2-yl dodecanoate, 2-phenylethyl oxo(phenyl)acetate, 3,7-dimethylocta-2,6-dien-1-yl oxo(phenyl)acetate, (Z)-hex-3-en-1-yl oxo(phenyl)acetate, 3,7-dimethyl-2,6-octadien-1-yl hexadecanoate, bis(3,7-dimethylocta-2,6-dien-1-yl)succinate, (2E,6Z)-2,6-nonadienyl hexadecanoate, (2E,6Z)-2,6-nonadienyl tetradecanoate, (2E,6Z)-2,6-Nonadienyl dodecanoate, (2-((2-methylundec-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(3-methyl-4-phenethoxybut-3-en-1-yl)benzene, (3-methyl-4-phenethoxybut-3-en-1-yl)benzene, 1-(((Z)-hex-3-en-1-yl)oxy)-2-methylundec-1-ene, (2-((2-methylundec-1-en-1-yl)oxy)ethoxy)benzene, 2-methyl-1-(octan-3-yloxy)undec-1-ene, 1-methoxy 4-(1-phenethoxyprop-1-en-2-yl)benzene, 1-methyl-4-(1-phenethoxyprop-1-en-2-yl)benzene, 2-(1-phenethoxyprop-1-en-2-yl)naphthalene, (2-phenethoxyvinyl)benzene, 2-(1-((3,7-dimethyloct-6-en-1-yl)oxy)prop-1-en-2-yl)naphthalene, (2-((2-pentylcyclopentylidene)methoxy)ethyl)benzene, 4-allyl-2-methoxy-1-((2-methoxy-2-phenylvinyl)oxy)benzene, (2-((2-heptylcyclopentylidene)methoxy)ethyl)benzene, 1-methoxy-4-(1-phenethoxyprop-1-en-2-yl)benzene, (2-((2-methyl-4-(2,6,6-trimethylcyclohex-1-en-1-yl)but-1-en-1-yl)oxy)ethyl)benzene, 1-methoxy-4-(2-methyl-3-phenethoxyallyl)benzene, (2-((2-isopropyl-5-methylcyclohexylidene)methoxy)ethyl)benzene, 1-isopropyl-4-methyl-2-((2-pentylcyclopentyl cyclopentylidene)methoxy)benzene, 2-methoxy-1-((2-pentylcyclopentylidene)methoxy)-4-propylbenzene, 2-ethoxy-1-((2-methoxy-2-phenylvinyl)oxy)-4-methylbenzene, 3-methoxy-4-((2-methoxy-2-phenylvinyl)oxy)benzaldehyde, 1-isopropyl-2-((2-methoxy-2-phenylvinyl)oxy)-4-methylbenzene, 4-((2-(hexyloxy)-2-phenylvinyl)oxy)-3-methoxybenzaldehyde or mixtures thereof.

[0046] By "perfuming adjuvant" is meant here an ingredient capable of imparting additional added effects, such as color, specific light resistance, chemical stability, etc. A detailed description of the nature and type of adjuvants customarily used in perfumed compositions cannot be exhaustive, but it should be mentioned that said ingredients are well known to the skilled artisan. As specific, non-limiting examples, one may mention: viscosity agents (e.g. surfactants, thickeners, gelling and / or rheology modifiers), stabilizers (e.g. preservatives, antioxidants, heat / light and / or buffers 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. By "fixatives", also referred to as "modifiers", is meant here an agent capable of influencing the manner in which the odor of the composition in which it is encapsulated, in particular the evaporation rate and intensity, can be perceived by the observer or user over time, compared to a similar perception in the absence of the modifier. In particular, modifiers make it possible to extend the time for which the fragrance is perceived.Non-limiting examples of suitable modifiers include methyl glucoside polyol, ethyl glucoside polyol, propyl glucoside polyol, isocetyl alcohol, PPG-3 myristyl ether, neopentyl glycol diethylhexanoate, sucrose laurate, sucrose dilaurate, sucrose myristate, sucrose palmitate, sucrose stearate, sucrose distearate, sucrose tristearate, hyaluronic acid disaccharide sodium salt, sodium hyaluronate, propylene glycol propyl ether, dicetyl ether, polyglycerin-4 ether, isoceteth-5, isoceteth-7, isoceteth-10, isoceteth-12, isoceteth-15, isoceteth-20, isoceteth-25, isoceteth-30, disodium lauroamphodipropionate, hexaethylene glycol monododecyl ether, and mixtures thereof, neopentyl glycol diisononanoate, cetearyl ethylhexanoate, panthenol ethyl ether, DL-panthenol, N-hexadecyl n-nonanoate, noctadecyl n-nonanoate, profragrance, cyclodextrin, encapsulation, and combinations thereof. Up to 20% by weight of the modifier, based on the total weight of the perfume composition, may be incorporated into the perfumed consumer product.

[0047] It is understood that a person skilled in the art is perfectly capable of designing the optimum formulation for the desired effect by mixing said components of the perfuming composition, simply by applying standard knowledge in the art and by trial and error methodology.

[0048] The compositions of the present invention consisting of at least one compound of formula (I) and at least one perfume carrier are particular embodiments of the present invention, as well as perfumed compositions comprising at least one compound of formula (I), at least one perfume carrier, at least one perfume base, and optionally at least one perfume adjuvant.

[0049] According to a particular embodiment, the perfuming composition is in the form of a microcapsule, preferably a microcapsule slurry, comprising at least one compound of formula (I). In one embodiment, at least one compound of formula (I) is encapsulated in a core-shell microcapsule, wherein at least one compound of formula (I) is contained in a core covered by a shell. In one embodiment, the shell of the microcapsule protects the compound of formula (I) from the environment. The shell is composed of a material capable of releasing at least one compound of formula (I). In one embodiment, the shell is composed of a material capable of releasing the compound of formula (I) upon breakage of the shell and / or by diffusion through the shell. The skilled person is familiar with the processes for preparing said microcapsules. The core of the core-shell microcapsule may further comprise, in addition to the compound of formula (I), at least one liquid carrier as defined above and / or at least one perfuming auxiliary ingredient as defined above. The core-shell microcapsule or the core-shell microcapsule slurry comprising at least one compound of formula (I) may be dispersed in at least one liquid carrier as defined above. Said liquid carrier may further comprise at least one compound of formula (I) and / or at least one perfuming co-ingredient as defined above.

[0050] According to certain embodiments, the shell of the microcapsule comprises a material selected from the group consisting of polyurea, polyurethane, polyamide, polyester, poly(meth)acrylate (i.e. polyacrylate and / or polymethacrylate), polysiloxane, polycarbonate, polysulfonamide, polymers of urea and formaldehyde, polymers of melamine and formaldehyde, polymers of melamine and urea, or polymers of melamine and glyoxal, and mixtures thereof. The shell may be hybrid, i.e. organic-inorganic, for example a hybrid shell composed of at least two types of inorganic particles that are crosslinked, or a shell resulting from a hydrolysis and condensation reaction of a polyalkoxysilane macromonomer composition.

[0051] According to certain embodiments, the core-shell microcapsules may be produced by different or more than one encapsulation method.

[0052] In preferred embodiments, the shells of the microcapsules may be selected, independently of one another, from the group of aminoplast, polyamide, polyester, polyurea and polyurethane shells and mixtures thereof.

[0053] In certain embodiments, the shell of the microcapsule comprises an aminoplast copolymer, such as melamine-formaldehyde or urea-formaldehyde or crosslinked melamine formaldehyde or melamine glioxal.

[0054] In certain embodiments, the shell of the microcapsule is polyurea-based, composed of, for example, but not limited to, an isocyanate-based monomer and an amine-containing crosslinker, such as guanidine carbonate and / or guanazole. Some polyurea microcapsules include 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 amines can be omitted.

[0055] In certain embodiments, 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 amount of colloidal stabilizer). In certain embodiments, the emulsifier is an anionic or amphiphilic biopolymer, which may be selected from the group consisting of gum arabic, soy protein, gelatin, sodium caseinate, and mixtures thereof.

[0056] In certain embodiments, the microcapsule shell is polyurethane-based, composed of, for example, but not limited to, polyisocyanates and polyols, polyamides, polyesters, and the like.

[0057] In certain embodiments, the microcapsules have a polymeric shell resulting from complex coacervation, where the shell is possibly crosslinked.

[0058] In a particular embodiment of the core-shell microcapsules, the core-shell microcapsules comprise an oily core comprising a hydrophobic active agent, preferably at least one compound of formula (I), and a composite shell comprising a first material and a second material, wherein the first material and the second material are different, the first material being a coacervate and the second material being a polymeric material.

[0059] In certain embodiments, the mass ratio of the first material to the second material is from 50:50 to 99.9:0.1.

[0060] In a particular embodiment, the coacervate comprises a first polyelectrolyte, preferably selected from among proteins (e.g. gelatin), polypeptides or polysaccharides (e.g. chitosan), most preferably gelatin, and a second polyelectrolyte, preferably selected from alginates, cellulose derivatives, guar gum, pectinates, carrageenans, polyacrylic and methacrylic acids or xanthan gum, or even vegetable gums, such as acacia gum (e.g. gum arabic), most preferably gum arabic.

[0061] The first material of the coacervate can be chemically hardened using a suitable cross-linking agent, such as glutaraldehyde, glyoxal, formaldehyde, tannic acid or genipin, or can be enzymatically hardened using an enzyme, such as transglutaminase.

[0062] The second polymeric material may be selected from the group consisting of polyurea, polyurethane, polyamide, polyester, polyacrylate, polysiloxane, polysulfonamide, polymers of urea and formaldehyde, polymers of melamine and formaldehyde, polymers of melamine and urea, or polymers of melamine and glyoxal, and mixtures thereof, preferably polyurea and / or polyurethane. The second material is preferably present in an amount of less than 3% by weight, preferably less than 1% by weight, based on the total weight of the microcapsule slurry.

[0063] The preparation of aqueous dispersions / slurries of core-shell microcapsules is well known to those skilled in the art. In certain embodiments, 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 methylol melamine, methylated methylol amine, imino melamine, and mixtures thereof. Suitable ureas include dimethylol urea, methylated dimethylol urea, urea resorcinol, and mixtures thereof. Materials suitable 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).

[0064] In certain embodiments of the core-shell microcapsules, the core-shell microcapsules are an oily core comprising a hydrophobic active substance, preferably at least one compound of formula (I), - optionally an inner shell composed of polymerized multifunctional monomers; - a biopolymer shell comprising proteins, wherein at least one of the proteins is crosslinked. Includes.

[0065] According to a particular embodiment, the protein is selected from the group consisting of milk proteins, caseinates such as sodium or calcium caseinate, casein, whey proteins, hydrolyzed proteins, gelatin, gluten, pea proteins, soy proteins, silk proteins and mixtures thereof, preferably sodium caseinate, most preferably sodium caseinate.

[0066] According to a particular embodiment, the proteins include sodium caseinate and globular proteins, preferably selected from the group consisting of whey proteins, beta-lactoglobulin, ovalbumin, bovine serum albumin, vegetable proteins, and mixtures thereof.

[0067] The protein is preferably a mixture of sodium caseinate and whey protein. According to certain embodiments, the biopolymer shell comprises a cross-linked protein selected from the group consisting of sodium caseinate and / or whey protein.

[0068] According to certain embodiments, the microcapsule slurry comprises: an oily core comprising a hydrophobic active substance, preferably at least one compound of formula (I), - an inner shell composed of polymerized multifunctional monomers, preferably polyisocyanates having at least two isocyanate functional groups; - a biopolymer shell comprising proteins, wherein at least one protein is crosslinked; - Optionally at least one outer mineral layer The microcapsule comprises at least one microcapsule comprising:

[0069] According to one embodiment, the sodium caseinate and / or whey protein are cross-linked proteins.

[0070] The mass ratio of sodium caseinate to whey protein is preferably 0.01-100, preferably 0.1-10, and more preferably 0.2-5.

[0071] In certain embodiments, the microcapsules are 1) combining a perfume oil with at least one polyisocyanate having at least two isocyanate functional groups to form an oil phase; 2) dispersing or dissolving an aminoplast resin and, optionally, a stabilizer in water to form an aqueous phase; 3) preparing an oil-in-water dispersion by combining an oil phase and a water phase, wherein the average droplet size is between 1 and 100 microns; 4) carrying out a curing step to form the walls of the microcapsules; and 5) Optionally, drying the final dispersion to obtain dried core-shell microcapsules. and wherein the aminoplast core-shell microcapsules are one shell, obtained by a process comprising:

[0072] In certain embodiments, the core-shell microcapsules are formaldehyde-free capsules. A typical process for the production of aminoplast formaldehyde-free microcapsule slurry is: 1) The following: a) Melamine or melamine and two NH 2 At least one C containing functional group 1 ~C 4 a polyamine component in the form of a mixture with a compound, b) Glyoxal, C 4-6 A mixture of 2,2-dialkoxy-ethanols and optionally glyoxalates, with a ratio of glyoxal / C of 1 / 1 to 10 / 1. 4-6 an aldehyde component in the form of a mixture having a molar ratio of 2,2-dialkoxy-ethanol; c) Protonic acid catalyst preparing an oligomeric composition comprising or obtained by reacting together the reaction products of 2) The droplet size is between 1 and 600 microns, and a. Oily substances, b. aqueous medium; c. at least one oligomeric composition obtained in step 1 d. at least one cross-linking agent selected from the following: I C 4 ~C 12 Aromatic or aliphatic diisocyanates or triisocyanates and their biurets, triuret, trimers, trimethylolpropane adducts and mixtures thereof, and / or ii. Formula Q-(Oxirane-2-ylmethyl) m [In the formula, m represents 2 or 3, and Q represents a C group optionally containing 2 to 6 nitrogen atoms and / or oxygen atoms. 2 ~C 6 Dioxirane or trioxirane compounds of the formula e. Optionally, two NH 2 C containing functional groups 1 ~C 4 compound preparing an oil-in-water dispersion comprising: 3) heating the dispersion. 4) Cooling the dispersion Includes.

[0073] The method is described in more detail in WO 2013 / 068255.

[0074] In certain embodiments of the core-shell microcapsules, the core-shell microcapsules are an oily core comprising a hydrophobic active substance, preferably at least one compound of formula (I), and - below Acyl chloride a first amino compound, and A second amino compound A polyamide shell comprising or derived from The polyamide core-shell microcapsules are

[0075] According to certain embodiments, the polyamide core-shell microcapsules are an oily core comprising a hydrophobic active substance, preferably at least one compound of formula (I), and A polyamide shell comprising: acyl chloride, preferably in an amount of 5-98%, preferably 20-98%, more preferably 30-85% (w / w); a first amino compound, preferably in an amount of 1 to 50% (w / w), preferably 7 to 40% (w / w), a second amino compound, preferably in an amount of 1 to 50% (w / w), preferably 2 to 25% (w / w), A stabilizer, preferably a biopolymer, preferably in an amount of 0-90%, preferably 0.1-75%, more preferably 1-70%. A polyamide shell comprising or derived from Includes.

[0076] According to certain embodiments, the polyamide core-shell microcapsules are an oily core comprising a hydrophobic active substance, preferably at least one compound of formula (I), and a polyamide shell comprising: Acyl chlorides, a first amino compound which is an amino acid, preferably an amino acid selected from the group consisting of L-lysine, L-arginine, L-histidine, L-tryptophan and / or mixtures thereof, a second amino compound selected from the group consisting of ethylenediamine, diethylenetriamine, cystamine and / or mixtures thereof, A biopolymer selected from the group consisting of casein, sodium caseinate, bovine serum albumin, whey protein, and / or mixtures thereof. or a polyamide shell obtained therefrom. Includes.

[0077] The first amino compound may be different from the second amino compound. Typically, the method for producing polyamide-based microcapsules comprises the following steps: a) dissolving at least one acyl chloride in a hydrophobic material, preferably a fragrance, to form an oil phase; b) dispersing the oil phase obtained in step a) into an aqueous phase containing a first amino compound to form an oil-in-water emulsion; c) carrying out a curing step to form polyamide microcapsules in the form of a slurry. wherein a stabilizer is added in the oil phase and / or in the water phase and at least one second amino compound is added to the water phase before the formation of the oil-in-water emulsion and / or to the oil-in-water emulsion obtained after step b).

[0078] In certain embodiments, the shell of the microcapsules is polyurea- or polyurethane-based, as described, for example, in WO 2007 / 004166, EP 2300146, and EP 2579976. Typically, a method for producing a polyurea- or polyurethane-based microcapsule slurry includes the steps of: 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 having an average droplet size of 1-500 μm, preferably 5-50 μm; and d) applying conditions sufficient to induce interfacial polymerization and form microcapsules in the form of a slurry. Includes.

[0079] In a particular embodiment, the microcapsules may be in the form of a powder, in particular obtained by subjecting the microcapsule slurry to a drying step, such as spray drying, to provide the microcapsules as such, i.e. in the form of a powder. It is understood that any standard method known to the skilled artisan for carrying out such drying may be applied. In particular, the slurry may be spray dried, preferably in the presence of a polymeric carrier material, such as polyvinyl acetate, polyvinyl alcohol, dextrin, natural or modified starch, gum arabic, vegetable gum, pectin, xanthan, alginate, carrageenan, or cellulose derivative, to provide the microcapsules in the form of a powder.

[0080] However, other drying methods may also be mentioned, such as extrusion, plating, spray granulation or fluidized bed processes, or drying at room temperature using materials (carriers, desiccants) that meet the specific criteria disclosed in WO 2017 / 134179.

[0081] According to a particular embodiment, said compositions comprise one or more compounds of formula (I) and allow the perfumer to produce accords or perfumes that exhibit the odour notes of the various compounds of the invention, thus creating new building blocks for the purpose of their production.

[0082] For reasons of clarity, it is also understood that any mixture obtained directly from a chemical synthesis, containing the compound of the invention as a starting, intermediate or final product, such as a reaction medium without sufficient purification, is not considered as a perfuming composition according to the invention, as long as said mixture provides the compound according to the invention in a form suitable for perfuming. Unpurified reaction mixtures are therefore generally excluded from the present invention, unless expressly stated otherwise.

[0083] The compounds of the invention may be advantageously used in all fields of modern perfumery, i.e. fine perfumery or functional perfumery, to positively impart or improve the odor of consumer products to which said (I) is added. Another object of the invention therefore consists in perfumed consumer products comprising, as perfuming ingredient, at least one compound of formula (I) as defined above.

[0084] The compounds of the invention can be added as such or as part of a perfuming composition according to the invention.

[0085] For reasons of clarity, "perfumed consumer product" is meant to indicate a consumer product that provides at least one pleasant odor effect to the surface or space to which the odor effect is applied (e.g. skin, hair, fabric, or home surface).In other words, the odorized consumer product according to the present invention is a odorized consumer product that comprises a functional preparation and optionally additional active substances corresponding to the desired consumer product, and an olfactory effective amount of at least one compound according to the present invention.For reasons of clarity, said odorized consumer product is a non-edible product.

[0086] The nature and type of ingredients of the perfumed consumer product, which in any case will not be exhaustive, does not warrant a more detailed description here, whereby a person skilled in the art can select the nature and type of ingredients of the perfumed consumer product on the basis of his general knowledge and according to the nature of the product and the desired effect.

[0087] Non-limiting examples of suitable perfumed consumer products include fine perfumes, such as refined fragrances, splashes or eau de parfums, colognes or shave or aftershave lotions; fabric care products, such as liquid or solid detergents, optionally in pod or tablet form, fabric softeners, liquid or solid scent boosters, dryer sheets, fabric refreshers, ironing water, paper, bleach, carpet cleaners, curtain care products; body care products, such as hair care products (e.g. shampoos, leave-on or rinse-off hair conditioners, hair dyes or hairsprays, color care products, hair shaping products), dental care products, disinfectants, intimate care products; cosmetic formulations (e.g. skin creams or lotions, vanishing creams or deodorants). or antiperspirants (e.g. sprays or roll-ons), depilatories, tanning or after-sun products, nail products, skin cleansers, make-up products); or skin care products (perfumed soaps, mousses, oils or gels for the shower or bath, or hygiene products, or foot / hand care products); air care products, such as air fresheners or "ready to use" powdered air fresheners that may be used in residential spaces (rooms, refrigerators, cupboards, shoeboxes or cars) and / or in public spaces (hall, hotel, mall, etc.); or home care products, such as mould removers, furniture care products, wipes, dish detergents or hard surface (e.g. floor, bath, sanitary or window washing) detergents; leather care products; car care products, such as polishes, waxes or plastic cleaners.

[0088] According to any embodiment of the present invention, the inventive flavored consumer product is characterized by having a pH of greater than or equal to 1. In particular, the inventive flavored consumer product has a pH of 1-12 or 1-8. More particularly, the inventive flavored consumer product has a pH of 1-6.

[0089] According to a particular embodiment, the perfumed consumer product of the present invention is in the form of a personal care, home care or fabric care consumer product, in particular a personal care, home care or fabric care consumer product that contains ingredients common to shower gels, shampoos, soaps, fabric detergents or softeners and multi-purpose cleaners. The main functional ingredients of the perfumed consumer product are surfactants and / or softener ingredients that can clean and / or soften fabrics and / or textiles of various natures, such as clothing, curtain fabrics, carpets and furniture fabrics, or other household surfaces, skin or hair, and are typically used with large amounts of water or water-based solvents. Thus, these are formulations in which the amount of water is typically 50-99% by mass of the perfumed consumer product, except for soaps or solid detergents, in which the amount of water is at most 20%.

[0090] A more detailed description of such fabric cleaner and / or softener formulations is not necessary here, and many descriptions of current liquid formulations can be found in detergent / fabric softener patents and other relevant literature, such as Louis Ho Tan Tai's textbook "Detergents et Produits de Soins Corporels, especially Chapters 1-7, Dunod, Paris, 1999", or other similar and / or more recent textbooks on the technology of liquid softener and all-purpose cleaner formulations. Patent publication WO 2010 / 105873 also describes typical current ingredients other than perfumes in such liquid products, especially on pages 9-21, and is cited as an example. Of course, many other examples of liquid detergent and / or fabric softener formulations can be found in the literature. Any such liquid formulations, i.e. liquid fabric cleaners or conditioners and / or all-purpose cleaners, may be used in the compositions described herein.

[0091] According to a particular embodiment of the present invention, the perfumed consumer product of the present invention is a liquid fabric softener comprising a fabric softener active base in an amount of 85-100% by weight, based on the total weight of the perfumed consumer product. The main component of the fabric softener active base is water or a water-based solvent. The fabric softener active base may comprise dialkyl quaternary ammonium salts, dialkyl ester quaternary ammonium salts, Hamburg esterquats, triethanolamine quats, silicones, and mixtures thereof. Optionally, the fabric softener active base may further comprise a viscosity modifier in an amount of 0.05-1% by weight, based on the total weight of the liquid base, the viscosity modifier being preferably selected from the group consisting of calcium chloride.

[0092] According to a particular embodiment of the present invention, the perfumed consumer product of the present invention is an all-purpose cleaner comprising an all-purpose cleaner active base in an amount of 85-100% by weight, based on the total weight of the perfumed consumer product. The main component of the all-purpose cleaner active base is water or a water-based solvent. The main component of the all-purpose cleaner active base is water or a water-based solvent. The all-purpose active base may comprise a linear alkylbenzene sulfonate (LAS) in an amount of 1-2%, a non-ionic surfactant in an amount of 2-4%, and an acid, such as citric acid, in an amount of 0.1-0.5%.

[0093] According to a particular embodiment of the present invention, the perfumed consumer product of the present invention is a liquid detergent comprising a liquid detergent active base in an amount of 85-100% by weight based on the total weight of the perfumed consumer product. The main component of the liquid detergent active base is water or a water-based solvent. The liquid detergent active base may comprise anionic surfactants such as alkyl benzene sulfonates (ABS), linear alkyl benzene sulfonates (LAS), secondary alkyl sulfonates (SAS), primary alcohol sulfates (PAS), lauryl ether sulfates (LES), sodium lauryl ether sulfate (SLES), methyl ester sulfonates (MES); non-ionic surfactants such as alkyl amines, alkanolamides, fatty alcohol poly(ethylene glycol) ethers, fatty alcohol ethoxylates (FAE), ethylene oxide (EO) and propylene oxide (PO) copolymers, amine oxides, alkyl polyglucosides, alkyl polyglucosamides; or mixtures thereof.

[0094] According to a particular embodiment of the present invention, the perfumed consumer product of the present invention is a solid detergent comprising a solid detergent active base in an amount of 85-100% by weight, based on the total weight of the perfumed consumer product. The solid detergent active base may comprise at least one surfactant selected from the group consisting of anionic, nonionic, cationic, zwitterionic surfactants and mixtures thereof. The surfactant in the solid detergent active base is preferably selected from the group consisting of linear alkene benzene sulfonic acids (LABS), sodium laureth sulfate, sodium lauryl ether sulfate (SLES), sodium lauryl sulfate (SLS), alpha olefin sulfonic acids (AOS), methyl ester sulfonic acids (MES), alkyl polyglycosides (APG), primary alcohol ethoxylates, in particular lauryl alcohol ethoxylates (LAE), primary alcohol sulfonic acids (PAS), soaps, and mixtures thereof. The solid detergent active base may contain further ingredients conventionally used in powder detergent consumer products, which are selected from the group consisting of bleaching agents, such as TAED (tetraacetylethylenediamine); buffers; builders, such as zeolites, sodium carbonate or mixtures thereof; soil release polymers or soil suspending polymers; granulated enzyme particles, such as cellulase, lipase, protease, mannanase, pectinase or mixtures thereof; corrosion inhibitors; antifoams; foam suppressors; dyes; fillers, such as sodium silicate, sodium sulfate or mixtures thereof; a hydrogen peroxide source, such as sodium percarbonate or sodium perborate; and mixtures thereof.

[0095] According to a particular embodiment of the present invention, the perfumed consumer product of the present invention is a shampoo or shower gel comprising a shampoo or shower gel active base in an amount of 85-100% by weight based on the total weight of the perfumed consumer product. The main component of the shampoo or shower gel active base is water or a water-based solvent. The active base of the shampoo shower gel may comprise sodium alkyl ether sulfate, ammonium alkyl ether sulfate, alkyl amphoacetic acid, cocamidopropyl betaine, cocamide MEA, alkyl glucoside and amino acid surfactant.

[0096] According to a particular embodiment of the present invention, the perfumed consumer product of the present invention is a soap bar comprising a soap active base in an amount of 85-100% by weight, based on the total weight of the perfumed consumer product. The soap bar active base may comprise a salt of a weak acid, which may typically be a fatty acid, and a salt of a strong base, such as sodium hydroxide.

[0097] Some of said perfumed consumer products may be aggressive media for the compounds of the invention, and therefore may need to be protected against premature degradation against suitable external stimuli, such as enzymes, light, heat or changes in pH, for example by encapsulation or by chemical bonding with other chemicals suitable for the release of the ingredients of the invention.

[0098] The proportions of the compounds according to the invention that may be incorporated into the various products or compositions vary in a wide range of values, depending on the nature of the article to be perfumed, as well as on the desired organoleptic effect and the nature of the auxiliary ingredients in a given base, when the compounds according to the invention are mixed with perfuming auxiliary ingredients, solvents or additives commonly used in the prior art.

[0099] For example, in the case of perfumed compositions, typical concentrations range from 0.001% to 30% or more by weight of the compound of the invention relative to the weight of the composition in which it may be incorporated. In the case of perfumed consumer products, typical concentrations range from 0.0001% to 10% or more by weight of the compound of the invention relative to the weight of the consumer product in which it may be incorporated.

[0100] Unless otherwise specified, all percentages refer to weight percent based on the total weight of the composition to which they refer.

[0101] The compounds of the invention can be prepared according to the methods described herein below.

[0102] Working Example The invention is described in further detail by the following examples, in which the abbreviations have their usual meaning in the art and the temperatures are given in degrees Celsius (° C.). NMR spectra were obtained using a 400 MHz ( 1 H) and 100MHz ( 13 C) operating with Bruker Avance II Ultrashield 400plus or 500MHz ( 1 H) and 125MHz ( 13 C) operated by Bruker Avance III500 or 600MHz ( 1 H) and 150MHz ( 13 C), and the spectra were internally referenced to tetramethylsilane at 0.0 ppm. 1 H NMR signal shifts are expressed in δ ppm and coupling constants (J) are expressed in Hz with the following multiplicities: d, doublet; t, triplet; q, quartet; m, multiplet; b, broad (indicating unresolved couplings) and were interpreted using Bruker Topspin software. 13 C NMR data are reported as chemical shifts δ ppm and hybridization from DEPT90 and DEPT135 experiments; C, quaternary; CH, methine; CH 2 , methylene; CH 3 , represented by methyl.

[0103] Example 1 Synthesis of a mixture containing 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-ol and 1-(4,4-dimethylcyclopent-1-en-1-yl)ethan-1-ol a) Step 1: Preparation of 3,3-dimethylhexanedioic acid In a 500 mL three-neck round-bottom flask equipped with a magnetic stir bar and reflux condenser, 230 mg of VO 3 NH 4 and 215 g of 60% HNO 3was charged. The solution was heated to 50°C and 75g of 4,4-dimethylcyclohexanol was carefully charged using a syringe pump: First, a few drops of 4,4-dimethylcyclohexanol were added to the pot and the evolution of red gas was observed almost instantly. Once the evolution of red NOx gas was observed, the remaining 4,4-dimethylcyclohexanol was added over 5 hours while the temperature rose to 60°C. After the addition was completed, the temperature dropped to 48°C. At this point, the reaction mixture was heated to 90-95°C for 1 hour to drive off the remaining NOx. The green solution was then allowed to slowly cool to room temperature overnight. The next morning, a white precipitate was observed and the slurry was further cooled to 0°C in an ice bath. The solid was filtered, washed with cold water and dried at 0.06 mbar / 75°C to give 64.5g of 3,3-dimethylhexanedioic acid as a white powder (97% purity, silylated with MSTFA). The mother liquor was concentrated to 115 g (from 440 g) on ​​a rotary evaporator and allowed to slowly crystallize at room temperature, followed by cooling in an ice-water bath to give an additional second crop of 9.3 g of 3,3-dimethylhexanedioic acid with a purity of 96%. Yield=70%.

[0104] Product 1 H and 13 The C NMR spectrum was consistent with the literature (Org. Lett. 2004, 6, 4411-4414).

[0105] b) Step 2: Preparation of 3,3-dimethylcyclopentan-1-one In a 100 mL cylindrical Kugelrohr flask, add 34.8 g of 3,3-dimethylhexanedioic acid and 1.62 g of Ba(OH). 2 The cylindrical flask was then charged with two other Kugelrohr valves in series and placed outside the furnace. The apparatus was rotated and the furnace was heated to atmospheric pressure and N 2 The mixture was heated to 270 °C under a stream of water. When it reached 265 °C, water vapor, CO 2, and other volatile distillates began to collect. After 2.5 hours, the furnace temperature was increased to 275°C and held at this temperature for an additional 6.5 hours until no further distillate was observed. The furnace was cooled, the distillate phase separated, and the aqueous phase was extracted twice with ether and combined with NaHCO 3 Wash with Na 2 SO 4 After removal of the ether, 15.78 g of a clear yellow oil of 99% purity was obtained.

[0106] Yield of 3,3-dimethylcyclopentan-1-one = 90% based on 82% conversion of 3,3-dimethylhexanedioic acid.

[0107] Product 1 H and 13 The C NMR spectrum was consistent with that reported in the literature (J. Org. Chem. 1996, 61, 8885-8896).

[0108] c) Step 3: Preparation of 1-ethynyl-3,3-dimethylcyclopentan-1-ol In a 250 mL three-neck round-bottom flask equipped with a magnetic stir bar and reflux condenser, add N 2 Charged 130 mL of 0.5 M ethynyl-MgBr solution in THF under atmosphere and cooled to 2° C. Then, 5 g of 3,3-dimethylcyclopentan-1-one was added over 5 min via syringe pump, allowing the temperature to rise to 8° C. The reaction was allowed to warm to room temperature and stirred for a total of 16.5 h. The reaction was quenched with 26 g of 10% HCl at 20° C. The phases were separated and the aqueous phase was extracted 3 times with ether, combined and diluted with NaHCO 3 Wash with Na 2 SO 4 The mixture was dried over silica gel, concentrated on a rotary evaporator, and distilled on a Kugelrohr (15-10 mbar / 100-150° C.) to give 5.1 g of 97% 1-ethynyl-3,3-dimethylcyclopentan-1-ol (84% yield).

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[0109] d) Step 4: Preparation of a mixture containing 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-one and 1-(4,4-dimethylcyclopent-1-en-1-yl)ethan-1-one A 2,000 mL, three-neck flask equipped with a magnetic stir bar and a reflux condenser was filled with N 2 Place in a 96% H2O2-free atmosphere. 2 SO 4 , 700 mL of heptane was charged and cooled to -25 °C. Using a syringe pump, 87 g of 1-ethynyl-3,3-dimethylcyclopentan-1-ol were introduced over 2.5 h. During the addition, the temperature varied from -25 °C to -17 °C. After the introduction of 1-ethynyl-3,3-dimethylcyclopentan-1-ol, GC analysis of the reaction mixture showed complete conversion. The dark mixture was poured onto ice. The aqueous phase was extracted with ether and NaHCO 3 Wash with Na 2 SO 4 The extract was dried over hexane and concentrated on a rotary evaporator to give 79.1 g of crude concentrate, which was then distilled on a short Vigreux column to give 70.3 g of a mixture containing 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-one (76%) and 1-(4,4-dimethylcyclopent-1-en-1-yl)ethan-1-one (20%), a yield of 80% of the mixture of the enones 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-one and 1-(4,4-dimethylcyclopent-1-en-1-yl)ethan-1-one.

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[0110] e) Step 5: Preparation of a mixture containing 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-ol and 1-(4,4-dimethylcyclopent-1-en-1-yl)ethan-1-ol A 1000 mL, three-necked round-bottom flask equipped with a magnetic stir bar and reflux condenser was filled with N 2Place under atmospheric pressure and add 9.4g of LiAlH 4 was charged, followed by 500 mL of anhydrous ether. The slurry was cooled to 4° C. and 70 g of a mixture containing 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-one and 1-(4,4-dimethylcyclopent-1-en-1-yl)ethan-1-one prepared in step 4 was introduced over 2 hours, with the temperature rising to a maximum of 7° C. At the end of the introduction, no starting material remained. The reaction was quenched to 0° C. and 9.4 mL of H 2 O was carefully added, followed by 9.4 mL of 5% NaOH and 28 mL of water. The slurry was stirred until off-white and filtered through a frit containing Celite. After concentration of the filtrate, 67.8 g of a crude mixture of 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-ol and 1-(4,4-dimethylcyclopent-1-en-1-yl)ethan-1-ol was obtained and used directly in the next step without further purification.

[0111] Example 2 Synthesis of a mixture containing 2(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol and 2(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol Into a 25 mL three-neck round-bottom flask equipped with a magnetic stir bar and a reflux condenser, 10 g of the mixture of 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-ol and 1-(4,4-dimethylcyclopent-1-en-1-yl)ethan-1-ol prepared in Example 1 and 4 mL of cyclohexane were placed. 2 The mixture was cooled to 0°C under reduced pressure. Then, 0.12 g of BF 3 OEt 2 was added in one shot and the temperature was allowed to rise to 1.5°C. Then 1.23g of i-butylene oxide dissolved in 0.83g of cyclohexane was added over 3 hours, and after stirring for an additional 20 minutes, NaHCO 3 The aqueous phase was extracted three times with ether, combined and 2 SO4 The mixture was dried over 1000 ml and concentrated on a rotary evaporator to give 11.73 g of crude product, which was distilled on a Fischer column to give 7.62 g of unreacted 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-ol and 1-(4,4-dimethylcyclopent-1-en-1-yl)ethan-1-ol, and 1.49 g of a mixture of 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol and 2-(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol (50% yield).

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[0112] Example 3 Synthesis of compounds of formula (I) and comparative compounds a) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl propionate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl propionate (compound of formula (I)) A 100 mL three-neck round bottom flask equipped with a magnetic stir bar and reflux condenser was charged with 15.4 g of the mixture of 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol and 2-(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol prepared in Example 2, 0.42 g of DMAP, and 50 mL of toluene. The solution was diluted with N 2 The mixture was heated to 50° C. under reduced pressure, and 12.2 g of propionic anhydride was charged in one shot, raising the reaction temperature to 66° C. within 5 minutes. The reaction was stirred at this temperature for 1 hour to complete the conversion of starting material. The reaction mixture was then added with 128 g of saturated NaHCO 3The mixture was poured slowly into a separatory funnel and stirred vigorously for 2 hours before being transferred to a separatory funnel. The phases were separated (pH 8) and the aqueous phase was extracted twice with toluene, combined and concentrated to give 20.51 g of crude concentrate. The crude concentrate was distilled on a Kugelrohr to give 20 g of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropionate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropionate in a ratio of 83 / 17. Yield=97%.

[0113] For NMR data see Example 3b), step 5.

[0114] b) Preparation of a composition containing only 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropionate (compound of formula (I)) Step 1 – Preparation of 2,2-dimethylhexanedial 1.9 g of 2,2-dimethylpent-4-enal, prepared by the procedure described in Org. Synth. Coll. Vol. 7, 1990, 177, was dissolved in 0.015 g of hydridocarbonyltris(triphenylphosphine)rhodium(I), 20 mL of ethyl acetate and 20 bar of CO / H 2 The mixture was hydroformylated in an autoclave at 90 °C using 1,2-dimethylhexanedial (linear product) to give a mixture containing 48% 2,2-dimethylhexanedial (linear product) and 35% 2,2,4-trimethylpentanedial (branched product). After removal of the solvent, the crude product was chromatographed on silica gel using a gradient dilution of pentane / ether from 99 / 1, 95 / 5, 90 / 10, 80 / 20 to 70 / 30, and the chromatographed material was bulb-to-bulb distilled to give 1.3 g of 2,2-dimethylhexanedial with a purity of 85%. 1 H and 13 The C NMR spectrum was consistent with that reported in the literature (J. Am. Chem. Soc. 2005, 127, 16778-16779).

[0115] Step 2 – Preparation of 3,3-dimethylcyclopent-1-ene-1-carbaldehyde Following the procedure described in Org. Synth. Coll. Vol. 8, 1993, 208, 0.89 g of crude 3,3-dimethylcyclopent-1-ene-1-carbaldehyde (74% purity) was prepared using 1.1 g of 2,2-dimethylhexanedial and used in the next step without further purification.

[0116] Step 3 – Preparation of 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-ol A 25 mL three-neck round-bottom flask equipped with a magnetic stir bar and reflux condenser was charged with 2.3 mL of 3 M MeMgI and heated with N 2 The flask was cooled to 0°C under atmosphere. 890 mg of 3,3-dimethylcyclopent-1-ene-1-carbaldehyde (74%) prepared in step 2 was dissolved in approximately 10 mL of ether and added in one shot to the Grignard flask, raising the pot temperature from 4 to 15°C. The reaction was allowed to warm to 20°C and stirred for a total of 1.5 hours before being quenched with 10% HCl. The crude product was diluted with ether, transferred to a 50 mL separatory funnel, the phases separated, extracted twice with ether, and diluted with NaHCO 3 Wash with Na 2 SO 4 The extract was dried over hexane and concentrated on a rotary evaporator to give 1.1 g of crude yellow oil. The oil was chromatographed on silica using 8 / 2 pentane / ether to give 1 g of 99% pure 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-ol. After bulb-to-bulb distillation, 670 mg of 99% pure 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-ol was obtained.

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[0117] Step 4 – Preparation of 2(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol Using pure 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-ol and the procedure described in Example 2 above, 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol was prepared.

[0118] Step 5 – Preparation of 2[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl propionate Using pure 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol and the procedure described in Example 3a above, 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropionate was prepared.

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[0119] c) Preparation of 2(1-(3,3-dimethylcyclopentyl)ethoxy)-2-methylpropylpropionate (comparative compound) 2.5 g of 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropionate prepared in Example 3b was dissolved in 18 mL of THF and charged with 50 mg of 5% Pd / C. The mixture was pressurized at 1 bar of H 2 Hydrogenation at rt overnight at rt gave complete conversion of the starting material to a 1 / 1 diastereomeric mixture of 2-(1-(3,3-dimethylcyclopentyl)ethoxy)-2-methylpropylpropionate. After filtering the catalyst and removing THF on a rotary evaporator, 2.51 g of concentrate was obtained. The concentrate was distilled on a Kugelrohr to give 2.5 g of 2-(1-(3,3-dimethylcyclopentyl)ethoxy)-2-methylpropylpropionate (diastereomeric mixture, 99% purity).

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[0120] d) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-oxoethylpropionate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-oxoethylpropionate 0.5 g of the mixture containing 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-ol and 1-(4,4-dimethylcyclopent-1-en-1-yl)ethan-1-ol prepared in Example 1, 0.49 g of methyl chloroacetate, 0.072 g of octyl 2 SnO and 10 mL of cyclohexane were charged to a 25 mL Schlenk tube equipped with a magnetic stir bar and a Dean-Stark trap and refluxed for 2 h. After concentrating the reaction mixture on a rotary evaporator, 0.9 g of crude chloroesters 1-(3,3-dimethylcyclopent-1-en-1-yl)ethyl 2-chloroacetate and 1-(4,4-dimethylcyclopent-1-en-1-yl)ethyl 2-chloroacetate were obtained. This was redissolved in 10 mL of NMP, charged with 0.5 g of sodium propionate, 0.05 g of NaI, and the slurry was stirred at 60 °C for 2 h to complete the conversion. Water was added to dissolve the solids, and the orange mixture was extracted first with cyclohexane (3 times) and then with ether (3 times). The combined extracts were then diluted with NaHCO 3 Wash with Na 2 SO 4 The crude concentrate was dried on a rotavap and concentrated. The crude concentrate was subjected to silica gel chromatography (60 g, 10 / 1 heptane / ethyl acetate) to obtain 0.79 g of a 95% pure composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-oxoethylpropionate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-oxoethylpropionate in a 75 / 25 ratio, respectively. It was distilled in a Kugelrohr still to obtain 0.658 g of a clear white distillate with a purity of 98%.

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[0121] e) Preparation of a composition of 2-(1-(3,3-dimethylcyclopentyl)ethoxy)-2-oxoethylpropionate (Comparative composition) Step 1 A mixture of 3.4 g of 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-ol and 1-(4,4-dimethylcyclopent-1-en-1-yl)ethan-1-ol was dissolved in 30 mL of THF and heated at 1 bar of H at room temperature. 2 35 mg of PtO 2 After filtering the catalyst through a bed of celite and removing the solvent, 3.5 g of 95% pure 1-(3,3-dimethylcyclopentyl)ethan-1-ol was obtained and used directly in the next step without further purification.

[0122] Step 2 A 25 mL three-neck round bottom flask equipped with a magnetic stir bar and Dean-Stark trap was charged with 1.4 g of crude 1-(3,3-dimethylcyclopentyl)ethan-1-ol prepared in step 1, 1.3 g of chloroacetic acid, 0.038 g of pTSA, and 10 mL of toluene. The mixture was heated to reflux for 2 h, resulting in complete conversion of the starting material to the two diastereomeric esters of 1-(3,3-dimethylcyclopentyl)ethyl 2-chloroacetate in a ratio of 48 / 45. The dark brown solution was cooled to 25 °C and 12 g of saturated NaHCO 3 The mixture was stirred for 5 minutes, after which the contents were transferred to a separatory funnel and the phases were separated. The aqueous phase was extracted once with toluene and combined with the remaining organic components and concentrated on a rotary evaporator to give 1.9 g of a crude 1 / 1 diastereomeric mixture of 1-(3,3-dimethylcyclopentyl)ethyl 2-chloroacetate, which was used directly in the next step.

[0123] Step 3 A 50 mL three-neck round bottom flask equipped with a magnetic stir bar and reflux condenser was charged with 1.8 g of crude 1-(3,3-dimethylcyclopentyl)ethyl 2-chloroacetate prepared in step 2, 15 g of NMP, 1.15 g of sodium propionate, and 0.12 g of NaI. The slurry was stirred at 20 °C for 64 h and then at 75 °C for 2 h to convert the starting material to 88% of a 1 / 1 diastereomeric mixture of 2-(1-(3,3-dimethylcyclopentyl)ethoxy)-2-oxoethylpropionate. The reaction mixture was cooled to 25 °C, charged with 15 mL of water, and transferred to a separatory funnel. The dark red solution was extracted five times with MTBE, and the combined extracts (light yellow) were diluted with 15% NaHSO. 3 Complete color removal by washing twice with NaHCO 3 Wash with Na 2 SO 4 The extract was dried over silica gel and concentrated on a rotary evaporator to give 1.88 g of crude 2-(1-(3,3-dimethylcyclopentyl)ethoxy)-2-oxoethylpropionate, which was distilled on a Kugelrohr to give 0.96 g of 96% pure 2-(1-(3,3-dimethylcyclopentyl)ethoxy)-2-oxoethylpropionate as a 1 / 1 mixture of two diastereomers.

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[0124] f) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butenoic acid and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butenoic acid A 25 mL round bottom flask equipped with a Dean-Stark trap was charged with 0.7 g of 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol and 2-(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol prepared in Example 2, 0.7 g of ethyl crotonate, 0.04 g of dibutyltin oxide, 10 mL of cyclohexane, and N 2 The mixture was heated under reflux for 18 hours and cooled to 20° C. The reaction mixture was concentrated on a rotary evaporator to give 0.89 g of crude product, which was chromatographed on silica using 3 / 1 pentane / ether as the solvent to give 0.546 g of a 99% product containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butenoate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butenoate. After distillation on a Kugelrohr, 0.529 g of a 99% product containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butenoate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butenoate was obtained. Yield=61%.

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[0125] g) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl methoxyacetate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl methoxyacetate A 25 mL Schlenk tube equipped with a Dean-Stark trap was charged with 0.7 g of 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol and 2-(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol prepared in Example 2, 1 g of methyl methoxyacetate, 0.04 g of dibutyltin oxide, and 10 mL of cyclohexane, and then quenched with N 2 The mixture was heated under reflux for 3 hours. The reaction mixture was cooled and concentrated on a rotary evaporator to give 1.09 g of concentrate. The concentrate was chromatographed on silica using 3 / 1 pentane / ether as the solvent to give 0.74 g of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl methoxyacetic acid and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl methoxyacetic acid, which was distilled on a Kugelrohr still to give 0.73 g of a 99% composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl methoxyacetic acid and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl methoxyacetic acid. Yield=91%.

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[0126] h) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylethyl carbonate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylethyl carbonate A 25 mL three-neck round-bottom flask equipped with a reflux condenser was charged with 0.6 g of 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol and 2-(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol prepared in Example 2, 0.016 g of DMAP, 0.4 g of triethylamine, and 10 mL of toluene, and heated at 40° C. in a water bath with N 2 The reaction mixture was cooled to 15 °C under reduced pressure. 0.325 mL of ethyl chloroformate was then charged in one shot and the reaction temperature was allowed to rise to 20 °C. After 1 hour and 45 minutes, an additional 0.8 mL of ethyl chloroformate was added, followed by 0.6 g of triethylamine. The slurry was stirred for a total of 69 hours, quenched by the addition of 10% HCl, transferred to a 50 mL separatory funnel, extracted with ether, and diluted with NaHCO 3 Wash with Na 2 SO 4 The mixture was dried on a rotavap and evaporated to give 0.69g of crude product, which was chromatographed on silica using 5 / 1 pentane / ether to give 0.318g of an 82% composition of 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylethyl carbonate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylethyl carbonate. The chromatographed material was distilled on a Kugelrohr to give 0.24g of a 98% composition of 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylethyl carbonate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylethyl carbonate. Yield=32%.

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[0127] i) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl(2R)-2-hydroxypropanoate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl(2R)-2-hydroxypropanoate Into a 25 mL three-neck round-bottom flask equipped with a mini Dean-Stark trap, 0.6 g of 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol and 2-(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol prepared in Example 2, 0.32 g of L-ethyl lactate, 0.033 g of dibutyltin oxide, and 10 mL of cyclohexane were placed. 2 The mixture was heated to reflux under reduced pressure. After 40 hours, the reaction was cooled to room temperature. The reaction mixture was cooled and concentrated on a rotary evaporator to give 1.11 g of crude product, which was chromatographed on silica using 2 / 1 pentane / ether as the solvent to give 0.4 g of a composition (92%) containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl(2R)-2-hydroxypropanoate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl(2R)-2-hydroxypropanoate. This was distilled on a Kugelrohr to give 0.365 g of distillate with a 98% composition of matter containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl(2R)-2-hydroxypropanoate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl(2R)-2-hydroxypropanoate. Yield=44%.

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[0128] j) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl(2S)-2-hydroxypropanoate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl(2S)-2-hydroxypropanoate As in Example 3i, except D-methyl lactate was used. Yield=45%.

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[0129] k) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-oxopropanoate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-oxopropanoate Into a 25 mL three-neck round-bottom flask equipped with a Dean-Stark trap, 0.7 g of 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol and 2-(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol prepared in Example 2, 0.63 g of methylpyruvic acid, 0.038 g of dibutyltin oxide, and 10 mL of cyclohexane were placed. 2The mixture was heated to reflux under reduced pressure. After 19 hours, the reaction mixture was cooled and concentrated on a rotary evaporator to give 1.06 g of crude concentrate, which was chromatographed on an 80 g silica cartridge using 3 / 1 pentane / ether as the solvent to give 0.458 g of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-oxopropanoate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-oxopropanoate. After distillation on a Kugelrohr, 0.4 g of a 99% pure composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-oxopropanoate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-oxopropanoate was obtained. Yield=62%.

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[0130] l) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylethyl oxalate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylethyl oxalate A 25 mL three-neck round bottom flask equipped with a mini Dean-Stark trap was charged with 0.7 g of 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol and 2-(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol prepared in Example 2, 0.9 g of ethyl oxalate, 0.037 g of dibutyltin oxide, 10 mL of cyclohexane, and N 2The mixture was heated under reflux for 1 hour and cooled to room temperature after 14.5 hours. After removing the solvent, 1.47 g of crude product was obtained. This was chromatographed on silica using 5 / 1 pentane / ether as the solvent to obtain 0.77 g of a mixture containing 10% ethyl oxalate and 89% of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylethyl oxalate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylethyl oxalate. It was distilled on a Kugelrohr to obtain 0.56 g of distillate with a composition of matter containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylethyl oxalate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylethyl oxalate of 99%. Yield=58%.

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[0131] m) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl cyclopropanecarboxylate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl cyclopropanecarboxylate A 50 mL three-neck round bottom flask equipped with a magnetic stir bar and a Dean-Stark trap was charged with 0.76 g of 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol and 2-(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol prepared in Example 2, 1 mL of methylcyclopropanecarboxylate, 100 mg of dibutyltin oxide, 20 mL of cyclohexane, and heated under N for 18 h. 2The mixture was heated to reflux at rt. The reaction mixture was cooled to room temperature and concentrated on a rotary evaporator to give 1.5 g of crude product, which was chromatographed on silica using 24 / 1 pentane / ether as solvent to give 0.47 g of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl cyclopropanecarboxylate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl cyclopropanecarboxylate. Yield=37%.

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[0132] n) Preparation of a composition containing 1-(3,3-dimethyl-1-cyclopenten-1-yl)ethyl malonate and 1-(4,4-dimethyl-1-cyclopenten-1-yl)ethyl malonate A 25 mL Schlenk tube equipped with a Dean-Stark trap was charged with 0.5 g of the mixture containing 1-(3,3-dimethylcyclopent-1-en-1-yl)ethan-1-ol and 1-(4,4-dimethylcyclopent-1-en-1-yl)ethan-1-ol prepared in Example 1, 1.6 g of diethyl malonate, 0.042 g of dibutyltin oxide, and 5 mL of cyclohexane, and then quenched with N. 2 The mixture was heated under reflux for 2.5 hours, then cooled and concentrated on a rotary evaporator. After the crude concentrate was distilled on a Kugelrohr, 0.52 g of a composition containing 1-(3,3-dimethyl-1-cyclopenten-1-yl)ethyl ethyl malonate and 1-(4,4-dimethyl-1-cyclopenten-1-yl)ethyl ethyl malonate was obtained at 96% yield. Yield=57%.

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[0133] o) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropiolate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropiolate A 50 mL round bottom flask equipped with a Dean-Stark trap was charged with 2 g of 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol and 2-(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol prepared in Example 2, 1.6 g of methyl propiolate, 0.12 g of dibutyltin oxide, 25 mL of cyclohexane, and N 2 The mixture was heated under reflux for 48 hours and then cooled to room temperature. After removal of the solvent, the crude product was chromatographed on silica using 95 / 5 pentane / ether as solvent to obtain 1.6 g of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropiolate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropiolate. It was distilled on a Kugelrohr to obtain 1.56 g of a distillate containing 99% of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropiolate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropiolate. Yield=62%.

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[0134] p) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butynoate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butynoate A 50 mL round bottom flask equipped with a Dean-Stark trap was charged with 1.85 g of 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol prepared in Example 2, 2 g of 2-(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol, 1.85 g of methyl butynoate, 0.12 g of dibutyltin oxide, 25 mL of cyclohexane, and N 2 The mixture was heated under reflux for 24 hours and cooled to room temperature. After removing the solvent, 2.76 g of crude product was obtained, which was chromatographed on silica using 95 / 5 pentane / ether as the solvent to obtain 1.59 g of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butynoate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butynoate. It was distilled on a Kugelrohr to obtain 1.55 g of a distillate containing 99% of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butynoate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl 2-butynoate. Yield=58%.

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[0135] q) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl acrylate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl acrylate A 50 mL round bottom flask equipped with a Dean-Stark trap was charged with 1 g of 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol and 2-(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol prepared in Example 2, 0.94 g of ethyl acrylate, 0.059 g of dibutyltin oxide, 15 mL of cyclohexane, and N 2 The mixture was heated under reflux for 28 hours and cooled to room temperature. After removal of the solvent, the crude product was chromatographed on silica using 95 / 5 pentane / ether as solvent to obtain 1 g of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl acrylate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl acrylate. It was distilled on a Kugelrohr to obtain 0.92 g of distillate containing 99% of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl acrylate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl acrylate. Yield=73%.

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[0136] r) Preparation of a composition containing 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl butyrate and 2-[1-(4,4-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropyl butyrate It was prepared according to the conditions reported in Example 3f) starting from a mixture containing ethyl butyrate and 2-(1-(3,3-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol prepared in Example 2 and 2-(1-(4,4-dimethylcyclopent-1-en-1-yl)ethoxy)-2-methylpropan-1-ol.

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[0137] Example 4 Preparation of the Perfuming Composition A perfuming composition for fine fragrance was prepared by mixing the following ingredients: [Table 2-1] [Table 2-2] [Table 2-3]

[0138] Addition of 2000 parts by weight of 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropionate prepared in Example 3b) to the composition imparts a musk character and at the same time results in a fruity raspberry scent. The musk character of the composition is perceived after 24 hours. The resulting composition corresponds to the composition of the invention used in the previous examples.

[0139] Addition of the same amount of 2-[1-(3,3-dimethylcyclopentyl)ethoxy]-2-methylpropylpropionate prepared in Example 3c) gave a dusty note with a slight musk connotation, weaker than the compound of the present invention, 2-[1-(3,3-dimethyl-1-cyclopenten-1-yl)ethoxy]-2-methylpropylpropionate. After 24 hours, only the dusty note was perceived.

[0140] Example 5 Preparation of Eau de Toilettes Containing the Compositions of the Invention An eau de toilette was prepared by adding 15% by weight of the composition of Example 4 of the invention to ethanol, relative to the total weight of the eau de toilette.

[0141] Example 6 Preparation of Liquid Detergents Containing Compounds of the Invention [Table 3] 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.

[0142] A liquid detergent is prepared by adding 0.5-1.5% by weight of the composition of Example 4 of the present invention, based on the total weight of the liquid detergent, to the unscented liquid detergent formulation of Table 1 with gentle shaking.

[0143] Example 7 Preparation of Fabric Softeners Containing Compounds of the Invention [Table 4] 1) Stepantex VL90 A Diester Quat;Supplier:Stepan 2) Proxel GXL; Supplier: Arch.

[0144] The fabric softener is prepared by weighing methyl bis[ethyl(tallow fatty acid)]-2-hydroxyethyl ammonium methyl sulfate, which is heated at 65° C., and water and 1,2-benzisothiazolin-3-one are placed in a reactor and heated at 65° C. under stirring. To the mixture, methyl bis[ethyl(tallow fatty acid)]-2-hydroxyethyl ammonium methyl sulfate is added. The mixture is stirred for 15 minutes and CaCl 2 Then, 0.5 to 2% by weight of the composition of Example 4 of the present invention is added based on the total weight of the softener. The mixture is stirred for 15 minutes and cooled to room temperature under stirring (viscosity measurement: result 35 + / - 5 mPas (shear rate 106 sec-1)).

[0145] Example 8 Preparation of a clear isotropic shampoo containing the composition of the present invention [Table 5] 1) Ucare Polymer JR-400, supplier: Noveon 2) Supplier: Schweizerhall 3) Glydant, source: 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.

[0146] Prepare shampoo by dispersing Polyquaternium-10 in water. Mix remaining ingredients of Phase A by adding each separately one after the other with good mixing after each addition. Add this premix to Polyquaternium-10 dispersion and mix for an additional 5 minutes. Then add premixed Phase B and premixed Phase C with stirring (Monomuls 90L-12 heated to melt in Texapon NSO IS). Add Phase D and Phase E with stirring. Adjust pH with citric acid solution until pH: 5.5-6.0 to give unscented shampoo formulation.

[0147] A fragranced shampoo is formulated by adding 0.4-0.8% by weight of the composition of Example 4 of the present invention, based on the total weight of the shampoo, to the unscented shampoo preparation of Table 3 with gentle shaking.

[0148] Example 9 Preparation of structured shower gels containing the compositions of the present invention [Table 6] 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; Brand and Supplier: GOLDSCHMIDT 5) KATHON CG; Trademark and supplier: ROHM&HASS.

[0149] A shower gel is formulated by adding 0.5-1.5% by weight of the composition of inventive example 4, based on the total weight of the shower gel, to the unscented shower gel formulation of Table 4 with gentle shaking.

[0150] Example 10 Preparation of a clear shower gel containing the composition of the present invention [Table 7] 1) EDETA B POWDER; Trademark and Supplier: BASF 2) ZETESOL AO 328 U; Trademark and Supplier: ZSCHIMMER&SCHWARZ 3) TEGO-BETAIN F 50; Brand and Supplier: GOLDSCHMIDT 4) MERQUAT 550; Brand and Supplier: LUBRIZOL.

[0151] A clear shower gel is formulated by adding 0.5-1.5% by weight of the composition of inventive example 4, based on the total weight of the shower gel, to the unscented shower gel formulation of Table 5 with gentle shaking.

[0152] Example 11 Formulation of a milky shower gel containing the composition of the present invention [Table 8] 1) EDETA B POWDER; Trademark and Supplier: BASF 2) Texapon NSO IS; Trademark and Supplier: Cognis 3) MERQUAT 550; Brand 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.

[0153] A clear shower gel is formulated by adding 0.5-1.5% by weight of the composition of inventive example 4, based on the total weight of the shower gel, to the unscented shower gel formulation of Table 6 with gentle shaking.

[0154] Example 12 Pearlescent Shampoo Formulations Containing the Compositions of the Invention [Table 9] 1) EDETA B Powder, supplier: BASF 2) Jaguar C14 S, supplier: Rhodia 3) Ucare Polymer JR-400, supplier: Noveon 4) Sulfetal LA BE, supplier: Zschimmer&Schwarz 5) Zetesol LA, Supplier: Zschimmer&Schwarz 6) Tego Betain F 50, supplier: Evonik 7) Xiameter MEM-1691, supplier: Dow Corning 8) Lanette 16, supplier: BASF 9) Comperlan 100, Supplier: Cognis 10) Cutina AGS, Supplier: Cognis 11) KathonCG, supplier: Rohm&Haas 12) D-Panthenol, supplier: Roche.

[0155] A shampoo is prepared by dispersing guar hydroxypropyltrimonium chloride and Polyquaternium-10 in water and tetrasodium EDTA. A 10% solution of NaOH (Phase B) is added once Phase A is homogeneous. Then premixed Phase C is added and the mixture is heated to 75°C. Phase D ingredients are added and mixed until homogeneous. The mixture is cooled. At 45°C, Phase E is added with mixing. Final viscosity is adjusted with 25% NaCl solution and pH is adjusted to 5.5-6 with 10% NaOH solution.

[0156] A fragranced pearlescent shampoo is formulated by adding 0.4-0.8% by weight of the composition of inventive Example 4, based on the total weight of the shampoo, to the unscented shampoo preparation of Table 7 with gentle shaking.

[0157] Example 13 Preparation of structured shower gels containing the compositions of the present invention [Table 10] 6) EDETA B POWDER; Trademark and Supplier: BASF 7) CARBOPOL AQUA SF-1 POLYMER; Trademark and supplier: NOVEON 8) ZETESOL AO 328 U; Trademark and Supplier: ZSCHIMMER&SCHWARZ 9) TEGO-BETAIN F 50; Brand and Supplier: GOLDSCHMIDT 10) KATHON CG; Trademark and supplier: ROHM&HASS.

[0158] A clear shower gel is formulated by adding 0.5-1.5% by weight of the composition of inventive example 4, based on the total weight of the shower gel, to the unscented shower gel formulation of Table 8 with gentle shaking.

[0159] Example 14 Preparation of anhydrous antiperspirant spray formulations containing the compositions of the present invention [Table 11] (1) Dow Corning® 345 Fluid; Supplier: Dow Corning (2) Aerosil® 200; Supplier: Evonik (3) Bentone® 38; Supplier: Elementis Specialities (4) Micro Dry Ultrafine;Supplier: Reheis.

[0160] Anhydrous antiperspirant spray formulation is prepared using a high speed mixer. Silica and Quaternium-18-Hectorite are added to the mixture of isopropyl myristate and cyclomethicone. Once fully swollen, aluminum chlorohydrate is added in small portions with stirring until the mixture is homogeneous and free of lumps. Then, perfume oil is added, which is the composition of Example 4 of the present invention.

[0161] Example 15 Preparation of Deodorant Spray Emulsion Formulations Comprising the Compositions of the Present Invention [Table 12]

[0162] The deodorant spray emulsion formulation is prepared by mixing and dissolving all ingredients according to the order in Table 10. Fill the aerosol canister, crimp and add the propellant. Aerosol fill: 40% active solution: 60% propane / butane, 2.5 bar.

[0163] Example 16 Preparation of Deodorant Stick Formulations Comprising the Compositions of the Invention [Table 13] (1) EDETA® B Power; Supplier: BASF (2) Cremophor® A25; Supplier: BASF (3) Tegosoft® APM; provided by Evonik (4) Irgasan® DP 300; Supplier: BASF.

[0164] The deodorant stick formulation is obtained by weighing all the ingredients of Part A and heating to 70-75°C. Ceteareth-25 is added after mixing and heating the other ingredients of Part A. Once Ceteareth-25 is dissolved, stearic acid is added. Part B is prepared by dissolving triclosan in 1,2-propylene glycol. The evaporated water is replaced. Then slowly, pour Part B into Part A while mixing. The perfume oil (Phase C), which is the composition of the invention of Example 4, is added while shaking gently. As stock, plastic bags are placed in a bucket and sealed after cooling. The moulds are filled at about 70°C.

[0165] Example 17 Preparation of Deodorant Roll-On Formulations Comprising the Compositions of the Present Invention [Table 14] (1) Natrosol® 250 H; Supplier: Ashland (2) Irgasan® DP 300; Supplier: BASF (3) Cremophor® RH 40; Supplier: BASF.

[0166] Part A is prepared by gradually sprinkling hydroxyethyl cellulose into water and stirring rapidly with a turbine until the hydroxyethyl cellulose is completely swollen and becomes a clear gel. Slowly pour Part B into Part A while continuing to stir until the entire mixture is homogenous. Then add Part C and Part D with gentle stirring.

[0167] Example 18 Preparation of a day cream-based O / W emulsion containing the composition of the present invention [Table 15] (1) Arlacel® 985; Supplier: Croda (2) Tefose® 2561; Supplier: Gattefosse (3) Biolip P 90;Supplier:Gattefosse (4) Mineral oil 30-40 CPS (5) Vaseline (6) Nipaguard® PO 5; Supplier: Clariant (7) PNC 400.

[0168] A day cream base O / W emulsion is prepared by heating phase A and phase B separately to 70-75°C. Phase A is added to phase B and vacuum is applied. The mixture is stirred and cooled to 55°C for 15 minutes. After cooling to room temperature, when the temperature reaches 45°C, phenoxyethanol (and) piroctone olamine (part C) are added. The mixture is stirred for 5 minutes, after which sodium carbomer (part D) and the perfume oil of the inventive composition of Example 4 (part E) are added. The mixture is stirred for 3 minutes and stirring is stopped for 15 minutes. When the temperature of the mixture reaches 30°C, stirring is resumed for another 15 minutes until the cream is homogeneous, glossy and free of lumps. If necessary, adjust the pH to 6.70-7.20 using Glydant, Phenonip or Nipaguard PO5 or to 6.30-7.00 using Nikkoguard.

Claims

1. Formula (I) 【Chemistry 1】 wherein one dotted line represents a carbon-carbon double bond and the other dotted line represents a carbon-carbon single bond; n is 0 or 1; X is C(=O) or C(Me) 2 group; R is a hydrogen atom, C 1-6 Alkyl group, C 1-6 Alkoxyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group or C 3-6 a cycloalkyl group, a C(═O)R′ group or a CH(OR″)R″ group, where R′ is C 1-3 Alkyl group or C 1-3 and R″ are each independently a hydrogen atom or a C 1-3 alkyl group).

10. The use of a compound of formula (I) in the form of any one of its stereoisomers or a mixture thereof as a perfuming ingredient.

2. When n is 0, R is C 1-6 The use according to claim 1, wherein the alkyl group is an alkoxyl group.

3. 2. The use according to claim 1, wherein n is 1.

4. The compound of formula (I) may be a compound of formula (II) 【Chemistry 2】 2. The use according to claim 1, wherein the compound is of the formula: [wherein the dotted line and R have the same meaning as defined in claim 1] in the form of any one of its stereoisomers or a mixture thereof.

5. R is C 1-3 Alkyl group, C 1-3 Alkoxyl group, C 2-3 Alkenyl group, C 2-3 Alkynyl group or C 3 a cycloalkyl group, or a C(═O)R′ group, where R′ is C 1-2 The use according to claim 1, wherein the aryl group is an alkyl group.

6. 2. The use according to claim 1, wherein R is an ethyl, propyl, ethoxy, prop-1-en-1-yl, 2-ethynyl or cyclopropyl group, or a C(=O)Me group.

7. 2. The use according to claim 1, wherein R is an ethyl group.

8. The compound of formula (I) is a compound of formula (III) 【Transformation 3】 2. The use according to claim 1, wherein the compound is in the form of any one of its isomers or a mixture thereof.

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

10. A compound of formula (I) as defined in claim 1.

11. below, i) at least one compound of formula (I) according to claim 10, 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 perfume composition comprising:

12. A scented consumer product comprising at least one compound of formula (I) according to claim 10 or a scented composition according to claim 11.

13. 13. The scented consumer product of claim 12, wherein the scented consumer product is a perfume, a fabric care product, a body care product, a cosmetic preparation, a skin care product, an air care product or a home care product.

14. The perfumed consumer product may be a fine perfume, splash or eau de parfum, cologne, shave or aftershave lotion, liquid or solid detergent, optionally in pod or tablet form, fabric softener, liquid or solid scent booster, dryer sheet, fabric refresher, ironing water, paper, bleach, carpet cleaner, curtain care product, shampoo, leave-on or rinse-off hair conditioner, hair dye, color care product, hair shaping product, dental care product, disinfectant, intimate care product, hair spray 14. The perfumed consumer product of claim 13, characterized in that it is a skin cream or lotion, a vanishing cream, a deodorant or antiperspirant, a depilatory, a tanning or sunscreen or after-sun product, a nail product, a skin cleanser, a makeup product, a scented soap, a shower or bath mousse, oil or gel, a foot / hand care product, a hygiene product, an air freshener, a "ready to use" powdered air freshener, a mold remover, a furnisher care, a wipe, a dish detergent or hard surface cleaner, a leather care product or a car care product.

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