Lily of the valley odorant

Abstract

The present invention relates to the use as perfuming ingredient of a compound of formula (I) in the form of any one of its stereoisomers or a mixture thereof, and wherein, when R 1 represents a C 1‑2 1-4 alkyl group, X represents a CHO group; or, when R 1 represents a hydrogen atom or a C 1‑2 1-4 alkyl group, X represents a CH(R 6 )CHO group; R 2 , R 3 , R 4 , R 5 and R 6 independently of one another represent a hydrogen atom or a C 1‑2 1-4 alkyl group, or R 3 and R 4 together represent an ethanediyl group; and, relative to position 1, the -C(R 3 )(R 4 )-CH(R 5 )-OH group is an ortho, meta, para substituent of the aromatic ring or a mixture thereof. Furthermore, the compound of formula (I) as part of a perfuming composition or of a perfumed consumer product is also part of the invention.

Description

Technical Field

[0001] This invention relates to the field of fragrances. More specifically, it relates to the use of compounds of formula (I) as flavoring agents, particularly for imparting fragrance. Types of odor. Furthermore, following the content mentioned herein, this invention includes the compounds of this invention as part of a fragrance composition or a fragranced consumer product. Background Technology

[0002] One of the key ingredients in the fragrance (cosmetic) industry is the component that imparts a floral scent, especially the aroma of lily of the valley. This fragrance is very popular and used in a variety of scented consumer products. (2-Methyl-3-[4-(2-methyl-2-propyl)phenyl]propanal, a trademark of Givaudan-Roure SA in Vergne, Switzerland) and (4 / 3-(4-hydroxy-4(methylpentyl)-3-cyclohexene-1-carboxaldehyde; source: International Flavors & Fragrances, USA) are all commonly used components in this target. It possesses the essence of lily of the valley and water, while It imparts a floral, lily-of-the-valley, and hydroxycitronellol fragrance, along with... The fragrance notes are completely different. However, both ingredients are restricted for various reasons.

[0003] Therefore, there is a need to develop novel fragrance components for lily of the valley, which can be used as... or Alternatives.

[0004] All developed hydroxyl All substitutes remain Tertiary alcohol functional groups present in it.

[0005] To the best of our knowledge, this invention discloses for the first time a flavored hydroxyl compound that can be used as a substitute for... It does not contain typical tertiary alcohol functional groups. Only one closely related structural analog of formula (I) is reported in WO 2017009175 as a fragrance ingredient, characterized by a pleasant and well-balanced floral, lily-of-the-valley, hydroxycitronellol odor profile, while the overall olfactory characteristics evoke one of the very familiar ingredients, Lyral. The analog is 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal, which resembles… That would have a tertiary alcohol, which has a chemical structure completely different from the compound of this invention.

[0006] The aforementioned prior art literature does not report or imply any sensory properties of the compound of formula (I), or any use of the compound in the field of fragrance. Summary of the Invention

[0007] This invention relates to compounds of formula (I), which can be used in... It imparts a floral-lily-of-the-valley fragrance in that direction.

[0008] Therefore, the first object of the present invention is the compound of formula (I),

[0009]

[0010] The compound is in the form of any one of its stereoisomers or a mixture of these stereoisomers, and wherein

[0011] When R 1 Representing C 1-2 When alkyl, X represents CHO group; or when R 1 Represents a hydrogen atom or C 1-2 When alkyl, X represents CH(R) 6 )CHO group.

[0012] R 2 R 3 R 4 R 5 and R 6 Each can independently represent a hydrogen atom or a carbon atom. 1-2 Alkyl; or R 3 and R 4 Combined, they represent ethylenedimethyl; and

[0013] Relative to position 1, -C(R) 3 (R) 4 )-CH(R 5 The -OH group is an ortho, meta, or para substituent of the aromatic ring, or a mixture thereof.

[0014] A second object of the present invention is a method for imparting, enhancing, improving or altering the odor characteristics of a flavored composition or a flavored article, the method comprising adding an effective amount of at least one compound of formula (I) as defined above to the composition or article.

[0015] A third object of the present invention is a compound of formula (I) as defined above, provided that 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(4-(2-hydroxyethyl)phenyl)propanal, 3-(4-(1-(hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(4-(1-hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(4-(2-hydroxypropyl)phenyl)propanal, 3-(4-(1-(hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(3-(1-(hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(3-(1-(hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2-(1-(hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(2-(1-(hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(2-(1-(hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(4-(1-hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(4-(1-hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(4-(1-hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(4-(2-hydroxyethyl)cyclopropyl)phenyl)butanal, 3-(4-(1-hydroxymethyl ... Aldehydes, 3-(3-(2-hydroxypropyl)phenyl)butanal, 3-(3-(2-hydroxypropyl)phenyl)propanal, 3-(3-(2-hydroxyethyl)phenyl)propanal, 3-(3-(2-hydroxyethyl)phenyl)butanal, 3-(3-(1-hydroxy-2-methylprop-2-yl)phenyl)butanal, 3-(3-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(2-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(2-(1-hydroxy-2-methylprop-2-yl)phenyl)butanal, 3-(2-(1-hydroxy-2-methylprop-2-yl)phenyl)butanal, 3-(2-(2-hydroxypropyl)phenyl)propanal, 3-(2-(2-hydroxypropyl)phenyl)propanal, 3-(4-(2-hydroxyethyl)phenyl)butanal and 3-(4-(2-hydroxypropyl)phenyl)butanal.

[0016] Another object of the present invention is a flavoring composition comprising:

[0017] i) at least one compound of formula (I) as defined above;

[0018] ii) at least one ingredient selected from the group consisting of a flavor carrier and a flavor base; and

[0019] iii) Optionally, at least one flavoring adjuvant.

[0020] The final object of the present invention is a flavored consumer product comprising at least one compound of formula (I) as defined above or a composition as defined above. Detailed Implementation

[0021] Surprisingly, it has now been discovered that compounds of formula (I) with primary or secondary alcohol functional groups possess a very interesting lily of the valley aroma profile, which is similar to... The overall olfactory characteristics are very similar, while also imparting an additional powdery flavor, which is particularly commendable. These compounds have never been publicly disclosed before.

[0022] Surprisingly, compounds with the following formula have now been found to be used as flavoring ingredients, for example, in addition to imparting... In addition to the typical scent profile, it also possesses a powdery fragrance note:

[0023]

[0024] The compound is in the form of any one of its stereoisomers or a mixture of these stereoisomers, wherein

[0025] When R 1 Representing C 1-2 When alkyl, X represents CHO group; or when R 1 Represents a hydrogen atom or C 1-2 When alkyl, X represents CH(R) 6 )CHO group;

[0026] R 2 R 3 R 4 R 5 and R 6 Each can independently represent a hydrogen atom or a carbon atom. 1-2 Alkyl; or R 3 and R 4 Combined, they represent ethylenedimethyl; and

[0027] Relative to position 1, -C(R) 3 (R) 4 )-CH(R 5 The -OH group is an ortho, meta, or para substituent of the aromatic ring, or a mixture thereof.

[0028] For clarity, the use of phrases such as "any of its stereoisomers" or similar expressions means as would be understood by those skilled in the art, that is, the compounds of the present invention can be pure enantiomers (if chiral), mixtures of enantiomers, pure diastereomers, mixtures of diastereomers; or mixtures thereof.

[0029] For clarity, by stating "relative to position 1, -C(R) 3 (R) 4 )-CH(R 5 The -OH group is an ortho, meta, para substituent or a mixture thereof on the aromatic ring, indicating that compounds of formula (I) can be in pure regiomeric form; for example, -C(R) is a substituent at position 1. 3 (R) 4 )-CH(R 5 -OH is a para-substituent on the aromatic ring, or the compound of formula (I) can be a mixture of regioisomers; for example, a mixture comprising: a compound of formula (I), wherein, relative to position 1, -C(R) is a para-substituent on the aromatic ring. 3 (R) 4 )-CH(R5 The -OH group is a para-substituent on an aromatic ring, and in compounds of formula (I), the -C(R) group is a para-substituent on the aromatic ring relative to position 1. 3 (R) 4 )-CH(R 5 The -OH group is a meta-substituent on the aromatic ring. When the compound of formula (I) is a mixture of regioisomers, X and R... 1 R 2 R 3 R 4 R 5 and R 6 It has the same meaning in each regional isomer.

[0030] According to any of the above embodiments of the present invention, the compound (I) is C 11 -C 18 Compound, preferably C 11 -C 15 .

[0031] According to any of the above implementation schemes, relative to position 1, -C(R) 3 (R) 4 )-CH(R 5 The -OH group can be a meta or para substituent on the aromatic ring.

[0032] According to any of the above embodiments, the compound used as a flavoring ingredient is a compound of the following formula:

[0033]

[0034] The compound is in the form of any one of its stereoisomers or a mixture of such stereoisomers, and wherein X, R 1 R 2 R 3 R 4 R 5 and R 6 It has the same meaning as above.

[0035] According to any of the above embodiments, the compound used as a flavoring ingredient is a compound of the following formula:

[0036]

[0037] R 1 R 2 R 3 R 4 R 5 and R 6 It has the same meaning as above.

[0038] According to any of the above embodiments, the compound used as a flavoring ingredient is a compound of the following formula:

[0039]

[0040] R 1 R 2 R 3 R 4 R 5 and R 6 It has the same meaning as above.

[0041] According to any of the above implementation schemes, R 1 R 2 R 3 R 4 R 5 and R 6 Each can be a hydrogen atom or a methyl group, independent of the others; R 3 and R 4 Combined, they represent ethylenedimethyl. Specifically, the R... 1 R 2 R 3 R 4 R 5 and R 6 One or two of them can represent hydrogen atoms, while the others can represent hydrogen atoms or methyl groups.

[0042] According to any of the above embodiments of the present invention, when X represents a CHO group, R 1 It can be C 1-2 Alkyl, or when X represents CH(R) 6 When the CHO group is present, R 1 It can be a hydrogen atom or a carbon atom. 1-2 Alkyl groups, while R 6 It has the same meaning as defined above. Preferably, when X represents a CHO group, R 1 It can be methyl, or when X represents CH(R) 6 When the CHO group is present, R 1 It can be a hydrogen atom or a methyl group. Even more preferably, when X represents a CHO group, R... 1 It can be methyl, or when X represents CH(R) 6 When the CHO group is present, R 1 It can be a hydrogen atom. Even more preferably, R 1 It can be a hydrogen atom, and X represents CH(R) 6 )CHO group.

[0043] According to any of the above embodiments of the present invention, R 2 It can be a hydrogen atom or a carbon atom. 1-2Alkyl group. Preferably, R 2 It can be a hydrogen atom or a methyl group. Even more preferably, R 2 It can be a hydrogen atom.

[0044] According to any of the above embodiments of the present invention, R 5 It can be a hydrogen atom or a carbon atom. 1-2 Alkyl group. Preferably, R 5 It can be a hydrogen atom or a methyl group. Even more preferably, R 5 It can be a hydrogen atom.

[0045] According to any of the above embodiments of the present invention, R 6 It can be a hydrogen atom or a carbon atom. 1-2 Alkyl group. Preferably, R 6 It can be a hydrogen atom or a methyl group. Even more preferably, R 6 It can be a hydrogen atom.

[0046] According to any of the above embodiments of the present invention, R 3 and R 4 It can be a hydrogen atom or a carbon atom. 1-2 Alkyl; R 3 and R 4 Combined, they represent ethylenedimethyl group. Preferably, R 3 and R 4 It can be a hydrogen atom or a methyl group; or R 3 and R 4 Combined, they represent ethylenedimethyl group. Preferably, R 3 It can be methyl, and R 4 It can be a hydrogen atom or a methyl group; or R 3 and R 4 Combined, they represent ethylenedimethyl group. Preferably, R 3 and R 4 It can represent methyl, or R 3 and R 4 Combined, they can represent ethylenedimethyl. Even more preferably, R... 3 and R 4 It can represent methyl.

[0047] According to any of the above embodiments of the present invention, the compound of formula (I) may be selected from the group consisting of 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)-2-methylpropanal, 3-(4-(2-hydroxyethyl)phenyl)propanal, 3-(4-(1-hydroxyprop-2-yl)phenyl)propanal, 3-(4-(1-(hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)butanal, 3-(4-(2-hydroxypropyl)phenyl)propanal, 3-(4-(3-hydroxy-2-methylbut-2-yl)phenyl)propanal, 3-(4-(3-hydroxybut-2-yl)phenyl)propanal and 3-(4-(1-hydroxy-2-methylprop-2-yl)-2-methylphenyl)propanal. Preferably, the compounds of the present invention can be selected from the group consisting of 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)-2-methylpropanal, 3-(4-(1-hydroxyprop-2-yl)phenyl)propanal, 3-(4-(2-hydroxypropyl)phenyl)propanal, 3-(4-(3-hydroxybut-2-yl)phenyl)propanal and 3-(4-(1-hydroxy-2-methylprop-2-yl)-2-methylphenyl)propanal. Even more preferably, the compounds of the present invention may be selected from the group consisting of 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(4-(1-hydroxyprop-2-yl)phenyl)propanal, 3-(4-(2-hydroxypropyl)phenyl)propanal and 3-(4-(3-hydroxybut-2-yl)phenyl)propanal. Even more preferably, the compounds of the present invention may be 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(4-(2-hydroxypropane)phenyl)propanal and 3-(4-(3-hydroxybut-2-yl)phenyl)propanal. Even more preferably, the compounds of the present invention may be 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal.

[0048] To the best of our knowledge, the compound of formula (I) reported above is novel and is therefore the object of this invention, provided that 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(4-(2-hydroxyethyl)phenyl)propanal, 3-(4-(1-(hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(4-(1-hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(4-(2-(hydroxypropyl)phenyl)propanal, 3-(4-(1-(hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(3-(1-(hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(3-(1-(hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2 ...3-(1-hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2-(1-hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(3-(1-hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2-(1-hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(3-(1-hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(3-(1-hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2-(1-hydroxymethyl)cyclopropyl)propanal, 3-(3-(1-hydroxymethyl)cyclopropyl)propanal, 3-(3-(1-hydroxymethyl)cyclopropyl)propanal, 3-(3-(1-hydroxymethyl)cyclopropyl)propanal, 3-(3-(1-hydroxymethyl)cyclopropyl)propanal, 3-(3-(2-hydroxypropyl)phenyl)butanal, 3-(3-(2-hydroxypropyl)phenyl)propanal, 3-(3-(2-hydroxyethyl)phenyl)propanal, 3-(3-(2-hydroxyethyl)phenyl)butanal, 3-(3-(1-hydroxy-2-methylprop-2-yl)phenyl)butanal, 3-(3-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(2-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(2-(1-hydroxy-2-methylprop-2-yl)phenyl)butanal, 3-(2-(1-hydroxy-2-methylprop-2-yl)phenyl)butanal, 3-(2-(2-hydroxypropyl)phenyl)propanal, 3-(4-(2-hydroxyethyl)phenyl)butanal and 3-(4-(2-hydroxypropyl)phenyl)butanal.

[0049] As a specific example of a compound of formula (I), 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal can be cited as a non-limiting example, which has a floral, lily-of-the-valley aroma and an overall olfactory character that strongly evokes a very familiar component. (4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; Source: International Flavors & Fragrances, USA). The industry has shown great interest in this striking similarity because... Its use is currently restricted due to allergens, and the industry is still awaiting olfactory alternatives to this ingredient. Additionally, the ingredient has powdery and creamy notes, which blend particularly well with musky notes.

[0050] According to a specific embodiment of the present invention, the compound of formula (I) is 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal.

[0051] When the odor of the compound of the present invention is compared with that of the prior art compound 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal, the compound of the present invention also has... It has a lily-of-the-valley scent, but is distinguished by its powdery notes. Contrary to existing technologies, the compounds of this invention are very harmonious with salicylic acid and musky notes. The compounds of this invention can be used as… The alternatives can also add powdery / creamy notes and enhance the musky notes of the composition. These differences make the compounds of the present invention and those of the prior art suitable for use as... It is a substitute, but it serves two different purposes: to impart different sensory impressions.

[0052] As described above, the present invention relates to the use of compounds of formula (I) as fragrance ingredients. In other words, it relates to a method or process for imparting, enhancing, improving, or altering the odor characteristics of a fragrance composition or a fragranced article or surface, the method comprising adding an effective amount of at least one compound of formula (I) to the composition or article, for example, to impart a typical fragrance note. It should be understood that the final hedonic effect may depend on the precise dosage and sensory characteristics of the compounds of the present invention; however, in any case, the addition of the compounds of the present invention will impart a typical tactile quality to the final product in the form of a fragrance note, touch, or aspect, depending on the dosage.

[0053] By “use of compound (I)”, it must also be understood herein to mean the use of any composition comprising at least one compound (I) and which may be advantageously used in the fragrance industry.

[0054] The composition, which can be advantageously used as a flavoring ingredient, is also an object of the present invention.

[0055] Therefore, another object of the present invention is a flavoring composition comprising:

[0056] i) at least one of the compounds of the present invention as defined above, used as a flavoring ingredient;

[0057] ii) at least one ingredient selected from the group consisting of a flavor carrier and a flavor base; and

[0058] iii) Optionally, at least one flavoring adjuvant.

[0059] By "fragrance carrier," we are referring here to a material that is almost neutral from a fragrance point of view, meaning it does not significantly alter the sensory properties of the fragrance ingredients. The carrier can be liquid or solid.

[0060] As liquid carriers, emulsion systems, i.e., solvent and surfactant systems, or solvents commonly used in fragrances, can be listed as non-limiting examples. A detailed description of the properties and types of solvents commonly used in fragrances is impossible to exhaust. However, solvents such as butanediol or propylene glycol, glycerol, dipropylene glycol and its monoethers, 1,2,3-propanetriyltriacetate, dimethyl glutarate, dimethyl adipate, 1,3-diacetoxypropyl-2-yl acetate, diethyl phthalate, isopropyl myristate, benzyl benzoate, benzyl alcohol, 2-(2-ethoxyethoxy)-1-ethanol, triethyl citrate, or mixtures thereof are the most commonly used. For compositions containing both fragrance carriers and fragrance bases, in addition to those detailed above, other suitable fragrance carriers may also be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins, such as those marketed under trademarks... Those known to the public (source: Exxon Chemical), or glycol ethers and glycol ether esters, such as those marketed under trademarks Those commonly known (source: Dow Chemical Company), or hydrogenated castor oil, such as those marketed as trademarks... RH 40, those that are well-known (Source: BASF).

[0061] A solid carrier is a material to which a flavoring composition or certain components of a flavoring composition can be chemically or physically bonded. Typically, such solid carriers are used to stabilize the composition or control the evaporation rate of the composition or certain components. Solid carriers are currently used in the art, and those skilled in the art know how to achieve the desired effect. However, as non-limiting examples of solid carriers, absorbent resins or polymers or inorganic materials, such as porous polymers, cyclodextrins, wood-based materials, organic or inorganic gels, clay, gypsum, talc, or zeolite, can be listed.

[0062] Other non-limiting examples of solid carriers include encapsulating materials. Examples of such materials may include wall-forming materials and plasticizers, such as monosaccharides, disaccharides or trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, proteins or pectins, or, as in references such as H. Scherz, Hydrokolloide: Stabilisatoren, Dickungs- und Geliermittel in Lebensmitteln, Band 2der Schriftenreihe Lebensmittelchemie, The materials listed in Behr's Verlag GmbH & Co., Hamburg, 1996. Encapsulation is a method well known to those skilled in the art and can be carried out, for example, by using techniques such as spray drying, agglomeration, or extrusion; or by encapsulation of coatings including agglomeration and composite agglomeration techniques.

[0063] Other non-limiting examples of solid carriers include core-shell encapsulations using resins of the type of amino plastics, polyamides, polyesters, polyureas, or polyurethanes, or mixtures thereof (all of which are well known to those skilled in the art), carried out by using polymerization-initiated phase separation methods, by interfacial polymerization, by techniques such as coagulation, or a combination of these techniques (all of which have been described in the prior art), and optionally in the presence of polymer stabilizers or cationic copolymers.

[0064] Resins can be produced by polycondensation of aldehydes (such as formaldehyde, 2,2-dimethoxyacetaldehyde, glyoxal, glyoxylic acid, or hydroxyacetaldehyde and mixtures thereof) with amines such as urea, benzoguanamine, glycoluryl, melamine, hydroxymethyl melamine, methylated hydroxymethyl melamine, guanidine, etc., and mixtures thereof. Alternatively, pre-formed resins can be used to hydroxylate polyamines, for example, under trademarks. (Source: Cytec Technology Corp.), Cy (Source: CytecTechnology Corp.) or (Source: BASF) Those that are commercially available.

[0065] Other resins are produced by the formation of trimers of polyols such as glycerol with polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, or phenyl diisocyanate, or biuret of hexamethylene diisocyanate, or trimers of phenyl diisocyanate with trimethylolpropane (as trade name). It is known that the polycondensation of (source: Mitsui Chemicals) produces a trimer of phenyl diisocyanate with trimethylolpropane and a biuret of hexamethylene diisocyanate.

[0066] Some research literature relating to the encapsulation of fragrances via the condensation of melamine resins with aldehydes is represented by articles such as those by K. Dietrich et al., Acta Polymerica, 1989, vol. 40, pages 243, 325, and 683, and 1990, vol. 41, page 91. These articles have described various parameters affecting the preparation of such core-shell microcapsules according to prior art methods, which are further detailed and exemplified in patent literature. US 4'396'670 of WigginsTeape Group Limited is a relevant early example of the latter. Since then, many other authors have enriched the literature in this field, and it is impossible to cover all published advances here, but general knowledge of this type of encapsulation is very important. More recent targeted publications, which also address suitable uses of such microcapsules, include articles by HYLee et al., Journal of Microencapsulation, 2002, vol. 19, pages 559-569, and International Patent Publication WO01 / 41915 or S. The article by Chimia et al., 2011, vol. 65, pages 177-181, is representative.

[0067] By "fragrance base," we are referring here to a composition that contains at least one flavoring ingredient.

[0068] The flavoring agent is not a compound of formula (I). Furthermore, by "flavoring agent," it refers herein to a compound used in flavoring preparations or compositions to impart a pleasurable effect. In other words, for a flavoring agent to be considered a flavoring agent, it must be recognized by those skilled in the art as capable of actively or pleasantly imparting or altering the odor of a composition, and not merely possessing an odor.

[0069] The nature and type of fragrance additives present in the base material are not guaranteed to be described in greater detail here, and are inexhaustible in any case. Those skilled in the art can select them based on their common sense and according to the intended use or application and the desired sensory effect. Generally, these fragrance additives belong to different chemical classifications, such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenes, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils, and the fragrance additives may be of natural or synthetic origin.

[0070] In particular, common flavoring ingredients may be cited because they have similar olfactory aromas, for example:

[0071] In particular, examples of flavoring agents commonly used in fragrance preparations can be listed, such as:

[0072] - Aldehyde components: decanal, dodecanal, 2-methylundecaldehyde, 10-undecenal, octanal and / or nonenal;

[0073] -Aromatic herbal ingredients: eucalyptus oil, camphor, eucalyptol, menthol and / or α-pinene;

[0074] - Balsam ingredients: coumarin, ethyl vanillin and / or vanillin;

[0075] - Citrus flavoring components: dihydromyrcenol, citral, orange oil, linalool acetate, citronellol, orange terpene, limonene, 1-p-menthene-8-yl acetate and / or 1,4(8)-p-menthadiene;

[0076] - Floral fragrance components: Methyl dihydrojasmonate, linalool, citronellol, phenethyl alcohol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexylcinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, β-ionone, methyl (2-methylamino)benzoate, (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, tricyclodecenyl acetate, geraniol, p-menth-1-en-8-ol, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate Mixtures of 1,1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, methyl jasmonate, 3-methyl-5-phenyl-1-pentanol, tricyclodecenyl propionate, geraniol acetate, tetrahydrolinalool, cis-7-p-menthol, (S)-2-(1,1-dimethylpropoxy)propionate, 2-methoxynaphthalene, 2,2,2-trichloro-1-phenylethyl acetate, 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde, pentylcinnamaldehyde, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, tricyclodecenyl isobutyrate, and / or methyl ionone isomers;

[0077] -Fruit flavor components: γ-undecyl lactone, 4-decyl lactone, ethyl 2-methylvalerate, hexyl acetate, ethyl 2-methylbutyrate, γ-nonyl lactone, allyl heptaate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-ethyl acetate and / or diethyl 1,4-cyclohexanedicarboxylate.

[0078] - Green fragrance components: 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styrax acetate, (2-methylbutoxy) allyl acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z)-3-octen-1-ol and / or 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one;

[0079] -Musk components: 1,4-dioxa-5,17-cycloheptadecanedione, pentadecene lactone, 3-methyl-5-cyclopentadecane-1-one, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopentyl[G]isochromene, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropyl ester, pentadecene lactone and / or (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methyl ester;

[0080] -Ingredients of costus root: 1-(octahydro-2,3,8,8-tetramethyl-2-naphthyl)-1-ethyl ketone, patchouli oil, terpene fraction of patchouli oil, (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, methyl cypressone, 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-octahydronaphthyl)ethyl-1-ketone and / or isoborneol acetate;

[0081] - Other components (e.g., amber, powdery, spicy, or watery): dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan and any stereoisomers thereof, piperaldehyde, anisaldehyde, eugenol, cinnamaldehyde, clove oil, 3-(1,3-benzodioxane-5-yl)-2-methylpropanal and / or 3-(3-isopropyl-1-phenyl)butanal.

[0082] The fragrance base according to the invention may not be limited to the aforementioned flavoring auxiliary ingredients, and many other such auxiliary ingredients are listed in the references in any case, such as S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or later versions thereof, or other works of similar nature, as well as a large number of patent documents in the fragrance industry. It should also be understood that the auxiliary ingredients may also be compounds known to release various types of flavoring compounds in a controlled manner.

[0083] By "fragrance adjuvant," we mean an ingredient that can impart additional benefits such as color, specific lightfastness, chemical stability, etc. A detailed description of the properties and types of adjuvants commonly used in fragrance compositions is impossible to exhaust, but it must be mentioned that the ingredients are well known to those skilled in the art. Specific, non-limiting examples include: viscous agents (e.g., surfactants, thickeners, gelling agents, and / or rheology modifiers), stabilizers (e.g., preservatives, antioxidants, heat / light stabilizers, and / or buffers or chelating agents, such as BHT), colorants (e.g., dyes and / or pigments), preservatives (e.g., antibacterial or antimicrobial or antifungal or antiirritant agents), abrasives, skin coolants, fixatives, insect repellents, ointments, vitamins, and mixtures thereof.

[0084] It is understood that those skilled in the art, by applying standard knowledge in the field and by mixing the above-mentioned components of the fragrance composition through trial and error, are fully capable of designing the optimal formulation for the desired effect.

[0085] In addition to flavoring compositions comprising at least one compound of formula (I), at least one fragrance carrier, at least one fragrance base and optionally at least one fragrance adjuvant, flavoring compositions comprising at least one compound of formula (I) and at least one fragrance carrier also constitute a specific embodiment of the present invention.

[0086] According to one specific embodiment, the above composition contains one or more compounds of formula (I), which enables fragrance manufacturers to prepare blends or fragrances with different aroma notes of the compounds of the present invention, thereby creating new tools for their work.

[0087] For clarity, it should also be understood that any mixture obtained directly from chemical synthesis (where the compounds of the present invention serve as starting materials, intermediates, or end products), such as reaction media that have not been adequately purified, cannot be considered a flavoring composition according to the present invention, provided that the mixture does not provide the compounds of the present invention in a suitable form for use in fragrances. Therefore, unless otherwise stated, unpurified reaction mixtures are generally excluded from the present invention.

[0088] Furthermore, compounds of formula (1) can also be advantageously used in all areas of modern fragrances (i.e., fine fragrances or functional fragrances) to actively impart or alter the odor of consumer products to which said compound (I) is added. Therefore, another object of the present invention includes a scented consumer product comprising at least one compound of formula (I) as defined above as a scenting ingredient.

[0089] The compound of formula (1) may be added as is or as part of the flavoring composition of the present invention.

[0090] For clarity, a "fragrant consumer product" refers to a consumer product intended to deliver at least one pleasant fragrance effect to the surface to which it is applied (e.g., skin, hair, fabric, or household surfaces). In other words, a fragrant consumer product according to the invention is a fragrant consumer product comprising a functional formulation and optional additional benefit agents corresponding to the desired consumer product, and an olfactorily effective amount of at least one compound of the invention. For clarity, the fragrant consumer product is a non-edible product.

[0091] The nature and type of ingredients in flavored consumer products are not guaranteed to be described in more detail here, and in any case, it is impossible to exhaustively describe them. Skilled personnel can select them based on their common sense and the characteristics of the product and the desired effect.

[0092] Non-restricted examples of suitable scented consumer products include perfumes, such as fine perfumes, sprays, or eau de perfumes, colognes, or shaving lotions or aftershaves; fabric care products, such as liquid or solid detergents, fabric softeners, liquid or solid scent enhancers, fabric fresheners, ironing solutions, paper products, bleach, carpet cleaners, and curtain care products; body care products, such as hair care products (e.g., shampoos, colorants or hairsprays, color-care products, hair styling products, and dental care products), disinfectants, and feminine hygiene products; cosmetic preparations (e.g., skin creams or lotions, cold creams, deodorants, or antiperspirants (e.g., sprays or roll-ons), depilatories, tanning agents, sunscreens or after-sun products, and nail products). Products such as skin cleansing products or cosmetics; or skin care products (such as soaps, shower gels, bath oils or bath liquids, or hygiene products or foot / hand care products); air care products, such as air fresheners or "ready-to-use" powder air fresheners, which can be used in home spaces (rooms, refrigerators, cabinets, shoes or cars) and / or public spaces (lobbies, hotels, shopping malls, etc.); or household care products such as mold removers, furniture care products, wipes, dishwashing liquids or hard surface cleaners (such as floors, bathrooms, sanitary ware or windows); leather care products; and car care products such as polishes, waxes or plastic cleaners.

[0093] Some of the aforementioned scented consumer products may represent corrosive media of the compounds of the present invention, and therefore may need to be protected from premature decomposition, for example by encapsulation or by chemically binding them to another chemical substance that is suitable for releasing the components of the present invention when subjected to suitable external stimuli, such as enzymes, light, heat or pH changes.

[0094] The proportion of compounds of formula (I) incorporated into various of the above-described articles or compositions can be varied over a wide range of numerical values. When the compounds according to the invention are mixed with flavoring agents, solvents or additives commonly used in the art, these values ​​depend on the nature of the article to be flavored and the desired sensory effect, as well as the nature of the auxiliary ingredients in the given base.

[0095] For example, in the case of flavored compositions, the typical concentration of the compounds of the present invention is 0.001 wt% to 10 wt%, or even more, based on the weight of the composition to which they are incorporated. In the case of flavored consumer products, the typical concentration of the compounds of the present invention is 0.0001 wt% to 2 wt%, preferably 0.0001 wt% to 1 wt%, or even more, based on the weight of the consumer product to which they are incorporated.

[0096] Compound (I) can be prepared according to the method described below.

[0097] Example

[0098] The invention will now be described in more detail by way of the following embodiments, wherein abbreviations have their usual meanings in the art, temperature is expressed in degrees Celsius (°C), and NMR spectral data in CDCl3 (unless otherwise stated) are... 1 H and 13 C was recorded using a 500MHz machine, the chemical shift δ was expressed in ppm relative to TMS as a standard, and the coupling constant J was expressed in Hz.

[0099] Example 1

[0100] Synthesis of compound (I)

[0101] ·3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal

[0102] Step 1: 2-(4-bromophenyl)-2-methylprop-1-ol:

[0103] A solution of methyl 2-(4-bromophenyl)-2-methylpropionate in THF (60 mL) (10 g, 39 mmol, 1 equivalent) was added dropwise to a suspension of lithium aluminum hydride (2.95 g, 78 mmol, 2 equivalents) in THF (70 mL) at 0 °C. After stirring at 0 °C for 1 hour, the reaction was quenched sequentially with 3 mL of water, 9 mL of 5% sodium hydroxide solution, and 3 mL of water. The mixture was filtered through a diatomaceous earth mat using diethyl ether as the eluent. The solvent was evaporated, and the residue was purified by ball-to-ball distillation (2–4 mbar, 130 °C) to give 2-(4-bromophenyl)-2-methylprop-1-ol (8.27 g, 93% yield).

[0104] 1H NMR: 1.30 (s, 6H), 3.57 (s, 2H), 7.25 (d, J = 8.6Hz, 2H), 7.45 (d, J = 8.6Hz, 2H).

[0105] 13 C NMR:145.6(s),131.4(d,2C),128.2(d,2C),120.1(s),72.8(t),39.9(s),25.2(q,2C).

[0106] Step 2: 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal:

[0107] A solution of 2-(4-bromophenyl)-2-methylprop-1-ol (5.0 g, 21.8 mmol, 1 equivalent) and N-cyclohexyl-N-methylaminocyclohexylamine (5.5 mL, 24.0 mmol, 1.1 equivalent) in DMF (44 mL) was degassed and stirred for 20 min under argon atmosphere. Allyl alcohol (1.63 mL, 24.0 mmol, 1.1 equivalent) and bis(dibenzylacetone)palladium(0) (125 mg, 0.22 mmol, 0.01 equivalent) were added, followed by 2-(tert-butylphosphino)-1-phenyl-1H-indole (221 mg, 0.66 mmol, 0.03 equivalent). The reaction was heated to 100 °C and held for 1 h. After cooling to room temperature, the solution was diluted with diethyl ether and washed three times with water. The organic layer was dried over sodium sulfate, and the solvent was evaporated. The residue (GC ratio of straight-chain to branched-chain products: 5.6:1) was purified by silica gel rapid chromatography column (heptane / AcOEt 7:3 to 65:35) and subjected to ball-to-ball distillation (0.35 mbar, 140 to 145 °C) to obtain the desired aldehyde as an oil (2.57 g, 57% yield).

[0108] 1 H NMR: 1.31 (s, 6H), 2.77 (t, J = 7.5Hz, 2H), 2.94 (t, J = 7.5Hz, 2H), 3.59 (s, 2H), 7.17 (d, J = 8.3Hz, 2H), 7.31 (d, J = 8.3Hz, 2H), 9.81 (t, J = 1.4Hz, 1H).

[0109] 13 C NMR:201.7(d),144.4(s),138.1(s),128.3(d,2C),126.5(d,2C),73.0(t),45.2(t),39.8(s),27.5(t),25.3(q,2C).

[0110] Minor isomer: 2-(4-(1-(hydroxymethyl-2-methylprop-2-yl)phenyl)propanal

[0111] 1 H NMR: 1.33 (s, 6H), 1.44 (d, J = 7.1Hz, 3H), 3.61 (s, 2H), 3.62 (m, 1H), 7.19 (d, J = 8.3Hz, 2H), 7.40 (d, J = 8.3Hz, 2H), 9.67 (d, J = 1.4Hz, 1H).

[0112] 13 C NMR:201.2(d),145.8(s),135.4(s),128.3(d,2C),127.0(d,2C),73.0(t),52.5(d),39.9(s),25.3(q,2C),14.5(q).

[0113] ·3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)-2-methylpropanal

[0114] A solution of 2-(4-bromophenyl)-2-methylprop-1-ol (2.0 g, 8.73 mmol, 1 equivalent) and N-cyclohexyl-N-methylaminocyclohexylamine (2.2 mL, 9.60 mmol, 1.1 equivalent) in DMF (17 mL) was degassed and stirred for 20 min under argon atmosphere. Methylallyl alcohol (0.81 mL, 9.60 mmol, 1.1 equivalent) and bis(dibenzylacetone)palladium(0) (50 mg, 0.087 mmol, 0.01 equivalent) were added, followed by 2-(tert-butylphosphino)-1-phenyl-1H-indole (88 mg, 0.26 mmol, 0.03 equivalent). The reaction was heated to 100 °C and held for 1 h. After cooling to room temperature, the solution was diluted with diethyl ether and washed three times with water. The organic layer was dried over sodium sulfate, and the solvent was evaporated. The residue was purified by silica gel rapid column chromatography (heptane / AcOEt 7:3), followed by ball-to-ball distillation (0.35 mbar, 145–150 °C) to obtain the desired aldehyde as an oil (1.49 g, 77% yield).

[0115] 1 H NMR:1.09(d,J=7.0Hz,3H),1.31(s,6H),2.59(Aof ABX,J=13.8,8.1Hz,1H),2.67(m,1H),3.06(B of ABX,J=13.8,6.1Hz,1H),3.59(s,2H),7.14(d,J=8.3Hz,2H),7.31(d,J=8.3Hz,2H),9.71(d,J=1.6Hz,1H).

[0116] 13 C NMR:204.5(d),144.5(s),136.6(s),129.1(d,2C),126.4(d,2C),73.0(t),48.0(d),39.8(s),36.1(t),25.3(q,2C),13.3(q).

[0117] ·3-(4-(1-hydroxypropyl-2-yl)phenyl)propanal

[0118] Step 1: Ethyl 2-(4-bromophenyl)propionate:

[0119] Lithium bis(trimethylsilyl)amide (1M in THF, 77mL, 77mmol, 1.1 equivalence) was added dropwise to a solution of ethyl 2-(4-bromophenyl)acetate (17.1 g, 70 mmol, 1 equivalent) in 235 mL of THF at -78 °C. After stirring at -78 °C for 15 min, methyl iodoform (5.5 mL, 88 mmol, 1.25 equivalence) was added dropwise. After stirring at -78 °C for 1 hour and 30 min, the reaction was quenched with saturated ammonium chloride solution. The mixture was extracted three times with diethyl ether, dried over sodium sulfate, and the solvent was evaporated. The residue was purified by silica gel rapid column chromatography (heptane / AcOEt 98:2) and subjected to ball-to-ball distillation (2–3 mbar, 140 °C) to give the desired ester as an oil (9.72 g, 54% yield).

[0120] Step 2: 2-(4-bromophenyl)prop-1-ol:

[0121] A solution of ethyl 2-(4-bromophenyl)propionate (4.8 g, 19 mmol, 1 equivalent) in THF (31 mL) was added dropwise to a suspension of lithium aluminum hydride (1.42 g, 37 mmol, 2 equivalents) in THF (31 mL) at 0 °C. After stirring at room temperature for 2 hours, the reaction was cooled to 0 °C and quenched sequentially with 1.4 mL of water, 4.2 mL of 5% NaOH solution, and 1.4 mL of water. The mixture was filtered through a diatomaceous earth mat using diethyl ether as the eluent, and the solvent was evaporated. The crude product was used as is in the next step.

[0122] Step 3: 3-(4-(1-hydroxypropyl-2-yl)phenyl)propanal:

[0123] A solution of 2-(4-bromophenyl)prop-1-ol (3.78 g, 17.6 mmol, 1 equivalent) and N-cyclohexyl-N-methylaminocyclohexylamine (4.42 mL, 19.3 mmol, 1.1 equivalent) in DMF (35 mL) was degassed and stirred for 20 min under argon atmosphere. Allyl alcohol (1.31 mL, 19.3 mmol, 1.1 equivalent) and bis(dibenzylideneacetone)palladium(0) (101 mg, 0.18 mmol, 0.01 equivalent) were added, followed by 2-(tert-butylphosphino)-1-phenyl-1H-indole (178 mg, 0.53 mmol, 0.03 equivalent). The reaction was heated to 100 °C and held for 1 h. After cooling to room temperature, the solution was diluted with diethyl ether and washed three times with water. The organic layer was dried over sodium sulfate, and the solvent was evaporated. The residue (GC ratio of straight-chain to branched-chain products: 5.6:1) was purified by silica gel rapid chromatography column (heptane / AcOEt 6:4) and subjected to ball-to-ball distillation (0.35 mbar, 140–145 °C) to obtain the desired aldehyde as an oil (1.92 g, 57% yield).

[0124] 1 H NMR:1.25(d,J=7.0Hz,3H),2.77(dt,J=7.6,1.3Hz,2H),2.93(t,J=7.6Hz,2 H),2.93(m,1H),3.67(d,J=6.8Hz,2H),7.16(m,4H),9.81(t,J=1.3Hz,1H).

[0125] 13 C NMR:201.7(d),141.7(s),138.6(s),128.5(d,2C),127.7(d,2C),68.7(t),45.2(t),42.0(d),27.7(t),17.6(q).

[0126] ·3-(4-(2-hydroxypropyl)phenyl)propanal

[0127] Step 1: 1-(4-bromophenyl)prop-2-ol:

[0128] A solution of 1-(4-bromophenyl)prop-2-one (5.00 g, 23.5 mmol, 1 equivalent) in THF (17 mL) was added dropwise to a suspension of lithium aluminum hydride (891 mg, 23.5 mmol, 1 equivalent) in 30 mL of THF at 0 °C. After stirring at 0 °C for 1 hour, the reaction was quenched successively with 0.9 mL of water, 2.7 mL of 5% sodium hydroxide solution, and 0.9 mL of water. The mixture was filtered through a diatomaceous earth mat using diethyl ether as the eluent. The solvent was evaporated, and the residue was purified by ball-to-ball distillation (2–4 mbar, 130 °C) to give 2-(4-bromophenyl)-2-methylprop-1-ol (4.91 g, 97% yield).

[0129] 1 H NMR:1.22(d,J=6.2Hz,3H),2.65(Aof ABX,J=13.6,7.8Hz,1H),2.72(BofABX,J=13.6,4.9Hz,1H),3.98(m,1H),7.08(d,J=8.3Hz,2H),7.42(d,J=8.3Hz,2H).

[0130] 13 C NMR (CDCl3, 125MHz): 137.5 (s), 131.6 (d, 2C), 131.1 (d, 2C), 120.3 (s), 68.7 (d), 45.0 (t), 22.9 (q).

[0131] Step 2: 3-(4-(2-hydroxypropyl)phenyl)propanal:

[0132] A solution of 1-(4-bromophenyl)prop-2-ol (3.0 g, 13.9 mmol, 1 equivalent) and N-cyclohexyl-N-methylaminocyclohexylamine (3.5 mL, 15.3 mmol, 1.1 equivalent) in DMF (28 mL) was degassed and stirred for 20 min under argon atmosphere. Allyl alcohol (1.04 mL, 15.3 mmol, 1.1 equivalent) and bis(dibenzylacetone)palladium(0) (80 mg, 0.14 mmol, 0.01 equivalent) were added, followed by 2-(tert-butylphosphino)-1-phenyl-1H-indole (141 mg, 0.42 mmol, 0.03 equivalent), and the reaction was heated to 100 °C for 1 h. After cooling to room temperature, the solution was diluted with diethyl ether and washed three times with water. The organic layer was dried over sodium sulfate, and the solvent was evaporated. The residue (GC ratio of straight-chain to branched-chain products: 5.6:1) was purified by silica gel rapid column chromatography (heptane / AcOEt 65:35), followed by ball-to-ball distillation (0.35 mbar, 140–145 °C) to obtain the desired aldehyde as an oil (1.39 g, 52% yield).

[0133] 1 H NMR:1.23(d,J=6.2Hz,3H),2.66(Aof ABX,J=13.5,7.9Hz,1H),2.74(BofABX,J=13.5,4.9Hz,1H),2.77(dt,J=7.6,1.2 Hz,2H),2.93(t,J=7.5Hz,2H),3.99(m,1H),7.14(s,4H),9.81(t,J=1.2Hz,1H).

[0134] 13 C NMR:201.6(d),138.4(s),136.5(s),129.6(d,2C),128.5(d,2C),68.8(d),45.3(t),45.2(t),27.7(t),22.8(q).

[0135] ·3-(4-(3-hydroxybut-2-yl)phenyl)propionaldehyde

[0136] Step 1: 3-(4-bromophenyl)but-2-ol:

[0137] To a THF (212 mL) solution of 1,4-dibromobenzene (15.0 g, 63.6 mmol, 1 equivalent), n-butyllithium (2.45 M, 26.0 mL, 63.6 mmol, 1 equivalent) was added dropwise at -78 °C. After stirring at -78 °C for 30 min, 2,3-dimethylethylene oxide (6.84 mL, 76 mmol, 1.2 equivalent) was added dropwise. After stirring at 78 °C for 30 min, boron trifluoride ether (9.67 mL, 76 mmol, 1.2 equivalent) was added dropwise. After stirring at -78 °C for 2 hours, the reaction was quenched with 10% w / w Na / K tartaric acid solution, and the mixture was allowed to reach room temperature overnight. The mixture was extracted three times with diethyl ether, and the combined organic extract was dried over sodium sulfate and the solvent was evaporated. The residue was purified by ball-to-ball distillation (125–130 °C, 2–4 mbar) to give 3-(4-bromophenyl)but-2-ol as an oil (2.85 g, 20% yield).

[0138] Step 2: 3-(4-(3-hydroxybut-2-yl)phenyl)propionaldehyde:

[0139] A solution of 3-(4-bromophenyl)but-2-ol (2.79 g, 12.2 mmol, 1 equivalent) and N-cyclohexyl-N-methylaminocyclohexylamine (3.07 mL, 13.4 mmol, 1.1 equivalent) in DMF (24 mL) was degassed and stirred for 20 min under argon atmosphere. Allyl alcohol (0.91 mL, 13.4 mmol, 1.1 equivalent) and bis(dibenzylacetone)palladium(0) (70 mg, 0.12 mmol, 0.01 equivalent) were added, followed by 2-(tert-butylphosphino)-1-phenyl-1H-indole (123 mg, 0.36 mmol, 0.03 equivalent). The reaction was heated to 100 °C and held for 1 h. After cooling to room temperature, the solution was diluted with diethyl ether and washed three times with water. The organic layer was dried over sodium sulfate, and the solvent was evaporated. The residue (GC ratio of straight-chain to branched-chain products: 5.3:1) was purified by silica gel rapid column chromatography (heptane / AcOEt 65:35), followed by ball-to-ball distillation (0.35 mbar, 140–145 °C) to obtain the desired aldehyde as an oil (691 mg, 27% yield).

[0140] 1 H NMR:1.08(d,J=6.3Hz,3H),1.30(d,J=7.0Hz,3H),2.71(s,1H),2.77(dt,J=7.5,1 .3Hz,2H),2.94(t,J=7.6Hz,2H),3.86(m,1H),7.13(s,4H),9.82(t,J=1.3Hz,1H).

[0141] 13 C NMR:201.7(d),142.2(s),138.3(s),128.3(d,2C),128.1(d,2C),72.3(d),46.7(d),45.2(t),27.7(t),21.0(q),16.0(q).

[0142] ·3-(4-(1-hydroxy-2-methylprop-2-yl)-2-methylphenyl)propanal

[0143] Step 1: Methyl 2-(4-bromo-3-methylphenyl)acetate:

[0144] Iodimethane (5.46 mL, 87 mmol, 2 equivalents) was added to a mixture of 2-(4-bromo-3-methylphenyl)acetic acid (10.0 g, 43.7 mmol, 1 equivalent) and potassium carbonate (9.05 g, 65.5 mmol, 1.5 equivalents) in acetone (87 mL), and the reaction was stirred at room temperature for 4 days. The acetone was evaporated, a saturated ammonium chloride solution was added, and the mixture was extracted three times with diethyl ether. The mixed organic extract was dried over sodium sulfate, and the solvent was evaporated. The residue was purified by ball-to-ball distillation (130–135 °C, 2–4 mbar) to give methyl 2-(4-bromo-3-methylphenyl)acetic acid as an oil (9.24 g, 87% yield).

[0145] Step 2: Methyl 2-(4-bromo-3-methylphenyl)-2-methylpropionate:

[0146] A solution of sodium bis(trimethylsilyl)amide (1M, 95mL, 95mmol, 2.3 equivalences in THF) was added dropwise to a solution of methyl 2-(4-bromo-3-methylphenyl)acetate (9.19g, 37.8mmol, 1 equivalent) in 126mL of THF at -78°C. After stirring at -78°C for 15 minutes, methyl iodine (7.09mL, 113mL, 3 equivalents) was added dropwise. After stirring at -78°C for 1 hour and 30 minutes, the reaction was quenched with saturated ammonium chloride solution. The mixture was extracted three times with diethyl ether, dried over sodium sulfate, and the solvent was evaporated. The residue was purified by silica gel rapid column chromatography (heptane / AcOEt 98:2) and subjected to ball-to-ball distillation (2–3 mbar, 140°C) to give the desired ester as an oil (9.10g, 89% yield).

[0147] Step 3: 2-(4-bromo-3-methylphenyl)-2-methylprop-1-ol:

[0148] A solution of methyl 2-(4-bromo-3-methylphenyl)-2-methylpropionate (9.05 g, 33.4 mmol, 1 equivalent) in THF (51 mL) was added to a suspension of lithium aluminum hydride (2.53 g, 66.8 mmol, 2 equivalents) in THF (60 mL) at 0 °C. After stirring at room temperature for 2 hours, the reaction was cooled to 0 °C and quenched sequentially with 2.5 mL of water, 7.5 mL of 5% NaOH solution, and 2.5 mL of water. The mixture was filtered through a diatomaceous earth mat using diethyl ether as the eluent, and the solvent was evaporated. The crude product was used as is for the next step.

[0149] Step 4: 3-(4-(1-hydroxy-2-methylprop-2-yl)-2-methylphenyl)propanal:

[0150] A solution of 2-(4-bromo-3-methylphenyl)-2-methylprop-1-ol (7.49 g, 27.1 mmol, 1 equivalent) and N-cyclohexyl-N-methylaminocyclohexylamine (6.83 mL, 29.8 mmol, 1.1 equivalent) in DMF (54 mL) was degassed and stirred for 20 min under argon atmosphere. Allyl alcohol (2.03 mL, 29.8 mmol, 1.1 equivalent) and bis(dibenzylacetone)palladium(0) (156 mg, 0.27 mmol, 0.01 equivalent) were added, followed by 2-(tert-butylphosphino)-1-phenyl-1H-indole (274 mg, 0.81 mmol, 0.03 equivalent). The reaction was heated to 100 °C and held for 1 h. After cooling to room temperature, the solution was diluted with diethyl ether and washed three times with water. The organic layer was dried over sodium sulfate, and the solvent was evaporated. The residue (GC ratio of straight-chain to branched-chain products: 25:1) was purified by silica gel rapid chromatography column (heptane / AcOEt 65:35) and subjected to ball-to-ball distillation (0.15 mbar, 140–145 °C) to obtain the desired aldehyde as an oil (3.56 mg, 60% yield).

[0151] 1 H NMR: 1.31(s,6H),2.32(s,3H),2.73(dt,J=7.7,1.2Hz,2H),2.91(d,J=7.7Hz,2H),3.58(s,2H),7.09(m,1H),7.15(m,2H),9.84(t,J=1.2Hz,1H).

[0152] 13 C NMR:201.7(d),144.5(s),136.2(s),135.8(s),128.6(d),128.3(d),124.1(d),73.0(t),43.9(t),39.7(s),25.4(q,2C),24.9(t),19.6(q).

[0153] Example 2

[0154] Preparation of Fragrance Composition

[0155] Women's perfume made by mixing the following ingredients:

[0156]

[0157]

[0158] *In dipropylene glycol

[0159] Adding 800 parts by weight of 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal obtained in Example 1 to the above composition, in place of 800 parts by weight of dipropylene glycol, imparts to the composition... The fragrance is characterized by floral lily-of-the-valley notes, with an additional creamy, powdery hint.

[0160] When the same amount of 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal was used instead of 800 parts by weight of dipropylene glycol in place of the compounds of the present invention, the resulting composition exhibited significant radiance, and the volume was very close to the floral and wet note twists associated with the addition of 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal. The sense of quantity gained over time.

[0161] 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal blends well with ozone, water and salicylate fragrance notes in the fragrance composition, with 3-(4-(1-hydroxy-2-methylpropyl-2-yl)phenyl)propanal blending particularly well with salicylate and musky fragrance notes.

[0162] Example 3

[0163] Preparation of Fragrance Composition

[0164] Men's fragrances are made by mixing the following ingredients:

[0165]

[0166]

[0167] *In dipropylene glycol

[0168] Adding 800 parts by weight of 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal obtained in Example 1 to the above composition, in place of 800 parts by weight of dipropylene glycol, imparts to the composition... The fragrance is characterized by floral lily-of-the-valley notes, with an additional subtle powdery character that is more creamy.

[0169] When the same amount of 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal was used instead of 800 parts by weight of dipropylene glycol in place of the compounds of the present invention, the resulting composition exhibited a significant aroma, and the volume was correlated with the floral and wet note transitions, very closely resembling that when 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal was added... The sense of quantity gained over time.

[0170] 3-[4-(2-hydroxy-2-methylpropyl)phenyl]propanal blends well with ozone, water and salicylate fragrance notes in the fragrance composition, with 3-(4-(1-hydroxy-2-methylpropane-2)-yl)phenyl)propanal blending particularly well with salicylate and musky fragrance notes.

[0171] Example 4

[0172] Preparation of perfumes containing the compositions of the present invention

[0173] A perfume is prepared by adding the composition of the present invention of Example 2 or 3, in an amount of 5% to 15% by weight relative to the total weight of the perfume, to ethanol under gentle shaking.

Claims

1. Uses of the compound of formula (I) as a flavoring ingredient, The compound is in the form of any one of its stereoisomers or a mixture of these stereoisomers, and wherein When R 1 Representing C 1-2 When alkyl, X represents a CHO group; or, when R 1 Represents a hydrogen atom or C 1-2 When alkyl, X represents CH(R) 6 )CHO group, R 2 R 3 R 4 R 5 and R 6 Each can independently represent a hydrogen atom or a carbon atom. 1-2 Alkyl; or R 3 and R 4 Combined, they represent ethylenedimethyl; and Relative to position 1, -C(R) 3 (R) 4 )-CH(R 5 The -OH group is a para-substituent of the aromatic ring.

2. The use according to claim 1, characterized in that, When X represents the CHO group, R 1 It is methyl; or when X represents CH(R) 6 When the CHO group is present, R 1 R is a hydrogen atom or a methyl group. 6 It has the same meaning as defined in claim 1.

3. The use according to claim 1, characterized in that, Compound (I) is a compound of the following formula: The compound is in the form of any one of its stereoisomers or a mixture of these stereoisomers, and wherein R 1 R 2 R 3 R 4 R 5 and R 6 It has the same meaning as above.

4. The use according to claim 1, characterized in that, R 2 R 5 and R 6 It can be a hydrogen atom or a methyl group.

5. The use according to claim 1, characterized in that, R 3 It is methyl, R 4 It is a hydrogen atom or a methyl group, or R 3 and R 4 Combined, they represent ethylenedimethylamine.

6. The use according to claim 1, characterized in that, Compound (I) is a compound of the following formula: The compound is in the form of any one of its stereoisomers or a mixture of these stereoisomers, and wherein R 1 R 2 R 5 and R 6 It has the same meaning as above.

7. The use according to claim 6, characterized in that, R 1 R 2 R 5 and R 6 Each hydrogen atom represents the others independently.

8. A method for imparting, enhancing, improving or altering the odor characteristics of a flavored composition or a flavored article, the method comprising adding an effective amount of at least one compound of formula (I) as defined in any one of claims 1 to 7 to the composition or article.

9. The compound of formula (I) as defined in any one of claims 1 to 7, provided that 3-(4-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(4-(2-(hydroxyethyl)phenyl)propanal, 3-(4-(1-(hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(4-(1-hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(4-(2-(hydroxypropyl)phenyl)propanal, 3-(4-(1-(hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(3-(1-(hydroxymethyl)cyclopropyl)phenyl)butanal, 3-(3-(1-(hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2 ...hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2-(1-hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2-(1-hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2-(1-hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2-(1-hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2-(1-hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2-(1-hydroxymethyl)cyclopropyl)phenyl)propanal, 3-(2-(1-hydroxymethyl) 3-(3-(2-hydroxypropyl)phenyl)butanal, 3-(3-(2-hydroxypropyl)phenyl)propanal, 3-(3-(2-hydroxyethyl)phenyl)propanal, 3-(3-(2-hydroxyethyl)phenyl)butanal, 3-(3-(1-hydroxy-2-methylprop-2-yl)phenyl)butanal, 3-(3-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(2-(1-hydroxy-2-methylprop-2-yl)phenyl)propanal, 3-(2-(1-hydroxy-2-methylprop-2-yl)phenyl)butanal, 3-(2-(1-hydroxy-2-methylprop-2-yl)phenyl)butanal, 3-(2-(2-hydroxypropyl)phenyl)propanal, 3-(4-(2-hydroxyethyl)phenyl)butanal and 3-(4-(2-hydroxypropyl)phenyl)butanal.

10. A flavoring composition comprising: i) at least one compound of formula (I) as defined in any one of claims 1 to 7; and ii) At least one ingredient selected from the group consisting of a flavor carrier and a flavor base.

11. The flavoring composition according to claim 10, characterized in that, The flavoring composition also contains at least one flavoring agent.

12. A flavored consumer product comprising at least one compound of formula (I) as defined in any one of claims 1 to 7 or a composition as defined in claim 10 or 11.

13. The scented consumer product according to claim 12, characterized in that, The scented consumer product is a perfume, fabric care product, body care product, skin care product, or air care product.

14. The scented consumer product according to claim 12, characterized in that, The scented consumer product is a cosmetic preparation or a household care product.

15. The scented consumer product according to claim 12, characterized in that, The scented consumer products include topical perfumes, eau de toilette, cologne, shaving lotion, aftershave, fabric softener, fabric freshener, ironing lotion, paper, bleach, carpet cleaner, curtain care products, shampoo, colorant, color care products, dental care products, disinfectant, feminine hygiene products, hair spray, deodorant, antiperspirant, hair removal product, tanning product, sunscreen, nail product, soap, shower mousse, bath oil, bath liquid, foot care products, hand care products, "ready-to-use" powder air freshener, mildew remover, furniture care product, dishwashing detergent, leather care products, or car care products.

16. The scented consumer product according to claim 12, characterized in that, The scented consumer product is a fine perfume, hair styling product, skin cleanser, or face cream.

17. The scented consumer product according to claim 12, characterized in that, The scented consumer product is a cosmetic, air freshener, liquid detergent, or solid detergent.

18. The scented consumer product according to claim 12, characterized in that, This scented consumer product is a hygiene product.

19. The scented consumer product according to claim 12, characterized in that, The scented consumer product is a wipe or a hard surface detergent.

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