Application of cyclic high-aroma folate as aromatic chemical

Abstract

The present invention relates to a compound of formula (I) as a fragrance chemical for imparting a wood, fruity, herbal, green leaf, root, citrus, bitter orange leaf, flower, damascenone, tobacco, ashtray, food, sweet, grass root, ionone, ambergris, a composition, the present invention relates to the use of a perfume, a fresh perfume, a natural perfume, a fir needle perfume, a camphor perfume, or any combination of two or more of these effects, and also to enhance and / or alter the aroma of a composition. The invention further relates to a composition comprising at least one compound of formula (I) and (i) at least one aromatic chemical different from a compound of formula (I) or (ii) at least one non-aromatic chemical carrier, or (iii) both (i) and (ii).

Description

Technical Field

[0001] The present invention relates to the use of compounds of formula (I) as aroma chemicals for imparting woody notes, fruity notes, herbal notes, green leaf notes, root notes, citrus notes, petitgrain notes, floral notes, damascena notes, tobacco notes, ashtray notes, gourmet notes, sweet notes, vanilla root notes, ionone notes, ambergris notes, fresh notes, natural notes, fir needle notes, camphor notes, or any combination of two or more of these effects to a composition and also for enhancing and / or modifying the aroma of the composition. The present invention further relates to a composition comprising at least one compound of formula (I) and (i) at least one aroma chemical different from the compound of formula (I) or (ii) at least one non-aroma chemical carrier, or (iii) both (i) and (ii). Background Art

[0002] Fragrance chemicals, especially perfumes, are of great interest particularly in the field of cosmetic, cleaning and laundry compositions.

[0003] Despite the existence of a large number of synthetic aromachemicals, there is a constant need for new components that can meet the numerous properties desired for the extremely diverse fields of application. These include, first of all, sensory properties, i.e. the compounds should have favorable olfactory properties. In addition, aromachemicals should also have additional positive secondary properties, such as, for example, efficient preparation methods, the possibility of better sensory attributes due to synergistic effects with other aromachemicals, higher stability under certain application conditions, better and higher fastness.

[0004] Such properties are of particular interest for compositions such as, for example, care compositions, hygiene articles, cleaning compositions, textile detergent compositions and compositions for fragrance dispensers.

[0005] Of particular interest are aroma chemicals that can impart one or more different sensory effects to the composition, thereby contributing to the rich and interesting sensory attributes of the composition, especially the olfactory attributes. In this regard, aroma chemicals that can impart woody notes, fruity notes, herbal notes, green notes, root notes, citrus notes, petitgrain notes, floral notes, damascone notes, tobacco notes, ashtray notes, gourmet notes, sweet notes, vanilla root notes, ionone notes, ambergris notes, fresh notes, natural notes, fir needle notes, camphor notes, or any combination of two or more of these effects are primarily of interest. In addition, in order to obtain a lasting odor effect in the composition and on the surface treated with the composition, firmness and persistence are of particular interest.

[0006] However, the targeted search for substances with certain and different sensory properties, such as a certain smell, is extremely difficult, since even small changes in the chemical structure can lead to large changes in sensory properties, such as smell and / or flavor. Therefore, the search for new aroma chemicals is in most cases difficult and laborious without knowing whether a substance with the desired smell and / or flavor will actually be found.

[0007] One object of the invention claimed herein is to provide substances which can be used as aroma chemicals in compositions, either alone or as a mixture, in particular odor-intensive substances with a pleasant odor are sought. In addition, they should be combinable with other aroma chemicals, thereby allowing the creation of novel advantageous sensory attributes and the use in compositions.

[0008] One object of the invention claimed herein is to provide a new aroma chemical having a pleasant olfactory effect; preferably, a combination of two or more of the effects selected from the group consisting of woody notes, fruity notes, herbal notes, green leaf notes, root notes, citrus notes, petitgrain notes, floral notes, damascena notes, tobacco notes, ashtray notes, gourmet notes, sweet notes, vanilla root notes, ionone notes, ambergris notes, natural notes, fir needle notes, camphor notes, or fresh notes.

[0009] A further object of the present invention is that the aromachemical should be obtainable from easily available starting materials, allowing its rapid and economical manufacture. Summary of the invention

[0010] These objects are achieved by providing the compounds of the invention and / or the mixtures of the invention. It has surprisingly been found that the compounds of the invention have a pleasant olfactory effect; preferably a combination of two or more of the effects selected from the group consisting of woody notes, fruity notes, herbal notes, green notes, root notes, citrus notes, petitgrain notes, floral notes, damascena notes, tobacco notes, ashtray notes, gourmet notes, sweet notes, vanilla root notes, ionone notes, ambergris notes, natural notes, fir needle notes, camphor notes, or fresh notes.

[0011] The first aspect of the invention claimed herein relates to compounds having formula (I)

[0012]

[0013] or a stereoisomer thereof for imparting a fragrance effect to a composition,

[0014] in,

[0015] X1 and X3 together form a double bond between the carbon atoms to which they are bonded, provided that X2 and X4 are hydrogen; or

[0016] X3 and X4 together form a double bond between the carbon atoms to which they are bonded, provided that X1 and X2 are hydrogen; or

[0017] X2 and X3 together form a double bond between the carbon atoms to which they are bonded, provided that X2 and X4 are hydrogen; or

[0018] X4 is OH, X1, X2 and X3 are all hydrogen,

[0019] And wherein R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0020] A second aspect of the invention claimed herein relates to the use of a compound of formula (I) for imparting a fragrance effect to a composition, the compound comprising:

[0021] At least one compound having formula (Ia)

[0022]

[0023] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0024] or at least one compound having formula (Ib)

[0025]

[0026] or at least one compound having formula (Ic)

[0027]

[0028] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0029] or at least one compound having formula (Id)

[0030]

[0031] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0032] or a mixture thereof;

[0033] in

[0034] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0035] A third aspect of the invention claimed herein relates to the use of a mixture of at least one compound of formula (Ia) for imparting a fragrance effect to a composition

[0036]

[0037] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0038] and at least one compound having formula (Ib),

[0039]

[0040] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0041] A fourth aspect of the invention claimed herein relates to the use of a mixture of at least one compound of formula (Ia) for imparting a fragrance effect to a composition

[0042]

[0043] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0044] at least one compound of formula (Ib),

[0045]

[0046] and

[0047] At least one compound having formula (Ic)

[0048]

[0049] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0050] in

[0051] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0052] A further aspect of the invention claimed herein relates to a method of imparting a fragrance effect to a composition, the method comprising at least the step of adding to the composition at least one compound having formula (I).

[0053] Another aspect of the invention claimed herein relates to the use of at least one compound having formula (I) for modifying the fragrance profile of a composition.

[0054] A further aspect of the invention relates to a mixture comprising at least one compound of formula (Ib),

[0055]

[0056] and

[0057] At least one compound having formula (IV)

[0058]

[0059] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0060] in,

[0061] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0062] Another aspect of the present invention relates to compounds having formula (Id)

[0063]

[0064] or its stereoisomers or a mixture of its stereoisomers for imparting a fragrance effect to a composition,

[0065] in

[0066] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0067] Another aspect of the invention claimed herein relates to a method for enhancing the aroma of a composition. The method comprises the step of mixing at least one compound of formula (I) with other ingredients such as, for example, at least one other aroma chemical different from the compound of formula (I) and / or at least one non-aroma chemical carrier to obtain an aroma chemical composition.

[0068] Yet another aspect of the invention claimed herein relates to a method of modifying the aroma of a chemical composition. The method comprises the step of incorporating at least one compound of the invention claimed herein into an aroma chemical composition to obtain an aroma modified aroma chemical composition.

[0069] Furthermore, compounds of formula (I) can be produced in good yield and purity by simple synthesis starting from readily available starting materials.Thus, the compounds of the invention claimed herein can be produced on a large scale and in a simple and cost-effective manner. DETAILED DESCRIPTION

[0070] The following detailed description is exemplary in nature and is not intended to limit the invention claimed herein or the application and use of the invention claimed herein. In addition, it is not intended to be bound by any theory presented in the foregoing technical field, background technology, summary of the invention or the following detailed description.

[0071] As used herein, the terms "comprising," "comprises," and "comprised of" are synonymous with "including," "includes," or "containing," "contains," and are inclusive or open-ended and do not exclude additional, unrecited members, elements, or method steps. It should be understood that, as used herein, the terms "comprising," "comprises," and "comprised of" encompass the terms "consisting of," "consists," and "consists of."

[0072] In addition, the terms "(a)", "(b)", "(c)", "(d)", etc. in the specification and claims are used to distinguish similar elements and are not necessarily used to describe a sequential order or a chronological order. It should be understood that the terms so used are interchangeable where appropriate, and that the embodiments of the subject matter described herein are capable of operating in other sequences than those described or shown herein. If the terms "(A)", "(B)" and "(C)" or AA), BB) and CC) or "(a)", "(b)", "(c)", "(d)", "(i)", "(ii)", etc. refer to steps of a method or use or an assay, there is no temporal or temporal continuity between these steps, that is, these steps can be performed simultaneously or there can be a time interval of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application described above or below.

[0073] In the following paragraphs, different aspects of the subject matter are defined in more detail. Unless explicitly indicated to the contrary, each aspect so defined can be combined with any one or more other aspects. In particular, any feature indicated as being preferred or advantageous can be combined with any one or more other features indicated as being preferred or advantageous.

[0074] References throughout this specification to "one embodiment" or "embodiment" or "preferred embodiment" mean that a particular feature, structure, or property described in conjunction with the embodiment is included in at least one embodiment of the invention claimed herein. Therefore, the phrases "in one embodiment" or "in a preferred embodiment" or "in a preferred embodiment" appearing in different places throughout this specification do not necessarily all refer to the same embodiment, but may refer to the same embodiment. In addition, in one or more embodiments, as will be apparent to those skilled in the art from this disclosure, the features, structures, or properties may be combined in any suitable manner. In addition, although some embodiments described herein include some but not other features included in other embodiments, the combination of features of different embodiments is intended to be within the scope of this subject matter and to form different embodiments, as will be understood by those skilled in the art. For example, in the appended claims, any of the claimed embodiments is used in any combination.

[0075] Furthermore, ranges defined throughout this specification also include the endpoints, ie, a range of 1 to 10 means that both 1 and 10 are included in the range. For the avoidance of doubt, the applicant shall be entitled to any equivalent means under applicable law.

[0076] In the context of the present invention, the term "aroma" refers to a sensory property and includes smell and / or flavor.

[0077] The term "aromachemical" means a substance used to obtain a sensory or organoleptic (used interchangeably herein) effect and includes its use to obtain an olfactory and / or flavor effect. The term "olfactory effect" or "note" (used interchangeably herein) means an odor effect without any positive or negative judgment, while the term "aroma effect" or "scent effect" or "fragrance effect" (used interchangeably herein) as used herein is related to an odor effect that is generally perceived as pleasant. Thus, "fragrance" or "aroma" means an aromachemical that primarily causes a pleasant odor effect. Flavor means an aromachemical that causes a taste effect.

[0078] As used herein, the term "fragrance composition" refers to a composition that causes fragrance. The term fragrance composition includes "odor composition" and / or "flavor composition". An odor composition is a composition that primarily causes an odor effect, and a flavor composition is a composition that primarily causes a taste effect.

[0079] The term "aroma attribute" refers to the overall aroma effect of aroma chemicals and is composed of the individual aroma effects of aroma chemicals.

[0080] The term odor composition includes "fragrance compositions" or "aroma compositions" (used interchangeably herein) which primarily cause an odor effect that is generally perceived as pleasant.

[0081] The general expressions "favorable sensory properties" or "favorable organoleptic properties" describe the niceness and clarity of the sensory effect delivered by the fragrance chemical. "Niceness" and "clarity" are terms familiar to those skilled in the art, such as perfumers. Niceness generally refers to a spontaneously induced, positively perceived, pleasant sensory effect. However, "niceness" is not necessarily synonymous with "sweetness". "Niceness" can also be the smell of musk or sandalwood. "Clearance" generally refers to a spontaneously induced sensory effect that causes reproducible reminders of the same specific thing for the same test panel. For example, a substance can have an odor that spontaneously reminds people of "apple": the odor will then be clearly "apple". If this apple odor is very pleasant, because the odor reminds people of, for example, sweet, fully ripe apples, the odor will be called "nice". However, the odor of a typical sour apple can also be clear. If these two reactions occur after smelling the substance, in this example, it is therefore a nice and clear apple odor, then this substance has particularly favorable sensory properties.

[0082] When the expression "combination of", "in combination with" or "combined with" is used herein to refer to a composition, method or use of two compounds, the fact that the two compounds need not be used in the form of a physical mixture of the compounds, but can be used (e.g., added) separately is taken into account. When the compounds are used separately, they can be used (e.g., added) sequentially (i.e., one after the other) or simultaneously (i.e., at substantially the same time) in any order.

[0083] The terms "boosting" or "boost" are used herein to describe the effect of enhancing and / or modifying the fragrance of a fragrance chemical or composition. The term "enhancing" includes an improvement in the niceness and / or clarity of a fragrance and / or an improvement in intensity. The term "modifying" includes a change in the fragrance attributes. The terms "niceness" and "clarity" are familiar to those skilled in the art, such as perfumers, and have corresponding meanings.

[0084] Intensity can be determined by threshold determination. The threshold of an odour is the concentration of a substance in the relevant gas space at which the odour effect no longer needs to be defined, but is still just perceptible to a representative test panel.

[0085] The booster effect is particularly desirable in fragrance compositions when applications characterized by a front note are desired, in which the odor is to be delivered particularly quickly and intensely, for example in deodorants, air fresheners or in the flavoring part of chewing gum.

[0086] The terms "the invention relates to" and "the invention is directed to" are used synonymously throughout the present invention.

[0087] The term "persistence" describes the evaporation behavior of an aroma chemical over time. Persistence can be determined, for example, by applying the aroma chemical to a test strip and by subsequent olfactory evaluation of the odor effect of the test strip. For aroma chemicals with high persistence, the time span over which the panel is still able to recognize the aroma effect is long.

[0088] The term "fastness" describes the interaction of fragrance chemicals with surfaces, such as skin or textiles, especially after subsequent treatment of the surface, such as washing. Fastness can be determined, for example, by washing textiles with a textile detergent composition comprising fragrance chemicals and then conducting an olfactory evaluation of the textiles directly after washing (wet textiles) and after prolonged storage of dry textiles.

[0089] The term "stability" describes the behavior of an aroma chemical upon contact with oxygen, light and / or other substances. Aroma chemicals with high stability retain their aroma properties over extended periods of time, preferably in a variety of compositions and under a variety of storage conditions.

[0090] In order to impart a long-lasting fragrance effect to the composition or the surface treated with the composition, the persistence, firmness and stability of the fragrance chemicals in the composition should preferably be high.

[0091] The term C1-C5-alkyl denotes a straight-chain or branched alkyl group containing 1 to 5 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl(isopropyl), butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl.

[0092] The term "C3-C5-alkenyl" refers to a straight-chain or branched unsaturated hydrocarbon group having 3 to 5 carbon atoms and having a double bond at any position.

[0093] Examples are "C3-C5-alkenyl" such as 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl.

[0094] The terms "cyclic homogeranate" and "ester of cyclic homogeranic acid" are used interchangeably in this specification.

[0095] As used herein, the term "compound (I)" or "compounds (I)" refers to one or more compounds having formula (I) including all stereoisomeric forms (stereoisomers) thereof in all ratios and / or salts thereof.

[0096] As used herein, the term "mixture" means a mixture of at least one compound having formula (Ia) or its stereoisomers or a mixture of its stereoisomers and / or at least one compound having formula (Ib) and / or a compound having formula (Ic).

[0097] Compounds of formula (Ia) and (1c) refer to compounds in their racemic form, or in one of their enantiomerically pure forms (R or S), or as a mixture of the two possible enantiomers in any ratio, wherein the ratio of enantiomers is in the range of 0.01:99.99 to 99.99:0.01.

[0098] The term "stereoisomer" is a general term for all isomers of a single compound as described by IUPAC, which differ only in the arrangement of their atoms in space, not in the way the atoms are connected. Thus, the term stereoisomer includes mirror image isomers (enantiomers), geometric (cis / trans or E / Z) isomers, and diastereomers. For the precise definition of these terms, see IUPAC definitions or Houben-Weyl E21a, Stereoselective Synthesis. Helmchen, RW Hoffmann, J. Mulzer, E. Schaumann (Hrsg.), 1995, G. Helmchen in 1-74: "Vocabulary and Nomenclature of Organic Stereochemistry". Possible isomers may exist as mixtures (i.e., racemates, cis / trans-mixtures or mixtures of diastereomers).

[0099] use

[0100] One embodiment of the invention claimed herein relates to a compound having formula (I)

[0101]

[0102] or a stereoisomer thereof for imparting a fragrance effect to a composition,

[0103] in,

[0104] X1 and X3 together form a double bond between the carbon atoms to which they are bonded, provided that X2 and X4 are hydrogen; or

[0105] X3 and X4 together form a double bond between the carbon atoms to which they are bonded, provided that X1 and X2 are hydrogen; or

[0106] X2 and X3 together form a double bond between the carbon atoms to which they are bonded, provided that X1 and X4 are hydrogen; or

[0107] X4 is OH, X1, X2 and X3 are all hydrogen,

[0108] in

[0109] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0110] In embodiments, the invention claimed herein relates to the use of a compound of formula (I) for imparting a fragrance effect to a composition, the compound comprising:

[0111] At least one compound having formula (Ia)

[0112]

[0113] or its stereoisomers or mixtures of its stereoisomers

[0114] or at least one compound of formula (Ib),

[0115]

[0116]

[0117] or at least one compound of formula (Ic),

[0118]

[0119] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0120] or at least one compound having formula (Id)

[0121]

[0122] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0123] or a mixture thereof;

[0124] in,

[0125] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0126] In another embodiment, the invention claimed herein relates to the use of a mixture of at least one compound having formula (Ia) for imparting a fragrance effect to a composition.

[0127]

[0128] or a stereoisomer thereof or a mixture of stereoisomers thereof; and

[0129] at least one compound of formula (Ib),

[0130]

[0131] in

[0132] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0133] Further embodiments of the invention claimed herein relate to the use of a mixture of at least one compound of formula (Ia) for imparting a fragrance effect to a composition

[0134]

[0135] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0136] at least one compound of formula (Ib),

[0137]

[0138] and at least one compound having formula (Ic)

[0139]

[0140] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0141] in

[0142] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0143] In an embodiment, R is selected from methyl, ethyl, propyl, butyl, isobutyl, isopropyl, 1-propenyl, or 2-propenyl.

[0144] Preferably, R is methyl, ethyl or 1-propenyl.

[0145] In the examples, the compound having the formula (Ia) and the compound having the formula (Ib) may be used alone or as a mixture in any ratio.

[0146] In another embodiment, the mixture of the compound having formula (Ia) and the compound having formula (Ib) is a mixture wherein the ratio of these compounds is in the range of 0.1:99.9 to 99.9:0.1.

[0147] In another embodiment, the mixture of the compound having formula (Ia) and the compound having formula (Ib) is a mixture wherein the ratio of these compounds is in the range of 0.1:99.9 to 99.9:0.1 or any number from 0.1 to 99.9.

[0148] In another embodiment, the mixture of a compound of formula (Ia) and a compound of formula (Ib) is a mixture wherein the ratio of these compounds is in the range of 1:99 to 99:1, preferably in the range of 20:80 to 80:20, or in the range of 30:70 to 70:30, or in the range of 40:60 to 60:40.

[0149] In another embodiment, the mixture of the compound having formula (Ia) and the compound having formula (Ib) is a mixture wherein the ratio of these compounds is a 50:50 ratio.

[0150] One skilled in the art can adjust the ratio of the compound of formula (Ia) to the compound of formula (Ib) to achieve a specific ratio in the range of 0.1:99.9 to 99.9:0.1 to impart a specific fragrance effect or effects to the composition.

[0151] In an embodiment, the compound having formula (Ia) refers to such a compound: in its racemic form, or in one of its enantiomerically pure forms (R or S), or as a mixture of two possible enantiomers in any ratio, wherein the ratio of enantiomers is in the range of 0.01:99.99 to 99.99:0.01.

[0152] In another embodiment, the mixture has a ratio ranging from 90:10 to 99.9:0.1, wherein the ratio represents the combined amount of the compound having formula (Ia) and the compound having formula (Ib) to the compound having formula (Ic).

[0153] In an embodiment, the mixture has the following ratios:

[0154] The ratio of [compound of formula (Ia) + compound of formula (Ib)]:[compound of formula (Ic)] is in the range of 90:10 to 99.9:0.1, preferably in the range of 93:7 to 99:1, and more preferably in the range of 95:5 to 99.9:0.1.

[0155] Preferred embodiments of the invention claimed herein relate to the use of at least one compound of formula (I) as an aroma chemical for imparting woody notes, fruity notes, herbal notes, green leaf notes, root notes, citrus notes, petitgrain notes, floral notes, damascena notes, tobacco notes, ashtray notes, gourmet notes, sweet notes, vanilla root notes, ionone notes, ambergris notes, fresh notes, natural notes, fir needle notes, camphor notes, or any combination of two or more of these notes to a composition.

[0156] In further embodiments, the invention claimed herein relates to the use of a compound having formula (I) for enhancing the fragrance of a composition.

[0157] In embodiments of the invention claimed herein, at least one compound having formula (I) is used as a flavor or fragrance composition.

[0158] In particular, at least one compound of formula (I) is used to impart a note to the composition selected from the group consisting of woody notes, fruity notes, herbal notes, green leaf notes, root notes, citrus notes, petitgrain notes, floral notes, damascena notes, tobacco notes, ashtray notes, gourmet notes, sweet notes, vanilla root notes, ionone notes, ambergris notes, fresh notes, natural notes, fir needle notes, camphor notes, or a combination of two or more notes.

[0159] In an embodiment, the invention relates to a mixture comprising at least one compound of formula (Ib),

[0160]

[0161] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0162] and

[0163] At least one compound having formula (IV)

[0164]

[0165] or a stereoisomer thereof or a mixture of stereoisomers thereof, wherein

[0166] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0167] In another embodiment, the present invention relates to the use of a mixture comprising at least one compound of formula (Ib),

[0168]

[0169] A compound having formula (Ib),

[0170] and

[0171] At least one compound having formula (IV)

[0172]

[0173] or a stereoisomer thereof or a mixture of stereoisomers thereof, wherein

[0174] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0175] In an embodiment, R is methyl.

[0176] In an embodiment, a mixture of a compound having formula (Ib) and a compound having formula (IV), wherein the weight ratio of the compound having formula (Ib) to the compound having formula (IV) is in the range of 90:10 to 99:1.

[0177] In an embodiment, the mixture of the compound having formula (Ib) and the compound having formula (IV) has a fragrance effect selected from leather or plastic or a combination thereof.

[0178] In an embodiment, the present invention relates to a compound having formula (Id)

[0179]

[0180] or a stereoisomer thereof for imparting a fragrance effect to a composition,

[0181] in

[0182] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0183] In an embodiment, the present invention relates to a compound having formula (Id)

[0184]

[0185] or the use of its stereoisomers,

[0186] wherein R is methyl.

[0187] Preferably, the compound of formula (I) is

[0188]

[0189] Suitable compositions as described above are, for example, compositions for personal care, home care, industrial applications and compositions for other applications, such as pharmaceutical compositions or crop protection compositions.

[0190] In an embodiment, the compound having formula (I) includes at least one compound having formula (Ia), at least one compound having formula (Ib) and at least one compound having formula (Ic), wherein the ratio of compound Ia, compound Ib and compound 1c respectively can vary between 0.1 and 99.9.

[0191] Preferably, the compounds of formula (I) according to the invention claimed herein are used in a composition selected from the group consisting of perfume compositions, body care compositions (including cosmetic compositions and products for oral and dental hygiene), hygiene articles, cleaning compositions (including dishwashing compositions), textile detergent compositions, compositions for fragrance dispensers, foods, food supplements, pharmaceutical compositions and crop protection compositions.

[0192] These compositions are described in the following paragraphs.

[0193] Composition

[0194] In embodiments, the invention claimed herein is directed to a composition comprising: at least one compound having formula (I), and

[0195] (i) at least one aroma chemical (X) different from the compound of formula (I), or

[0196] (ii) at least one non-aroma chemical carrier, or

[0197] (iii) Both (i) and (ii).

[0198] Preferably, in this embodiment, the composition comprises the compound having formula (I) in a total amount ranging from ≧0.01 wt.% to ≦70.0 wt.%, based on the total weight of the composition.

[0199] Preferably, the composition is a fragrance composition, more preferably a scent composition.

[0200] Aroma chemicals are distinct from compounds of formula (I).

[0201] In one embodiment, the mixture comprises at least one aroma chemical other than the compound having formula (I). Aroma chemicals other than the compound having formula (I) are also referred to as aroma chemicals (X).

[0202] Due to their physical properties, compounds of formula (I) can be combined well with aroma chemicals other than compounds of formula (I) and other conventional ingredients in fragrance compositions, in particular in flavor compositions. This allows, for example, the creation of fragrance compositions (preferably flavor compositions) with novel advantageous sensory attributes. In particular, as already explained above, these compounds can provide an accelerant effect for other aroma chemicals (such as spices).

[0203] The aroma chemicals (X) are preferably selected from the group consisting of:

[0204] Geranyl acetate, α-hexylcinnamaldehyde, 2-phenoxyethyl isobutyrate, dihydrogeranyl alcohol, methyl dihydrojasmonate, 4,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopenta[g]benzopyran, tetrahydrolinalool, ethyl linalool, benzyl salicylate, 2-methyl-3-(4-tert-butylphenyl)propanal, cinnamyl alcohol, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5-indenyl acetate and / or 4,7-methano-3a,4,5,6,7,7a-hexahydro-6-indenyl acetate, citronellol, citronellol acetate, tetrahydrogeraniol, vanillin, linalyl acetate, styroyl acetate, octahydro -2,3,8,8-tetramethyl-2-naphthylacetonone and / or 2-acetyl-1,2,3,4,6,7,8-octahydro-2,3,8,8-tetramethylnaphthalene, hexyl salicylate, 4-tert-butylcyclohexyl acetate, 2-tert-butylcyclohexyl acetate, α-ionone, α-methylionone, α-iso-methylionone, coumarin, terpineol acetate, 2-phenylethanol, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-carboxaldehyde, α-amylcinnamaldehyde, brazilic acid ethylene glycol ester, (E) and / or (Z)-3-methylcyclopentadecan-5-enone, 15-pentadecan-11-ene lactone and / or 15-pentadecan-12-ene lactone, 15-cyclodecane Pentadecanoic acid lactone, 1-(5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphthyl)ethanone, 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, cis-3-hexenyl acetate, trans-3-hexenyl acetate, trans-2 / cis-6-nonadienol, 2,4-dimethyl-3-cyclohexenecarboxaldehyde, 2,4,4,7-tetramethyloct-6-en-3-one, 2,6-dimethyl-5-heptene-1-al, borneol, 3-(3-isopropylphenyl)butyraldehyde, 2-methyl-3-(3,4-methylenedioxy)butyraldehyde 1,2-dimethyl-2-(4-(4-(tert-butyl)phenyl)-propanal, 3-(4-ethylphenyl)-2,2-dimethylpropanal, 7-methyl-2H-1,5-benzodioxepan-3(4H)-one, 3,3,5-trimethylcyclohexyl acetate, 2,5,5-trimethyl-1,2,3,4,4a,5,6,7-octahydronaphthalen-2-ol, 3-(4-tert-butylphenyl)-propanal, ethyl 2-methylpentanoate, ethoxymethoxycyclododecane, 2,4-dimethyl-4,4a,5,9b-tetrahydroindeno[1,2-d][1,3]dioxin, (2-tert-butylcyclohexyl) acetate and 3-[5,5,6-trimethylbicyclo[2.2.1]heptan-2-yl]cyclohexan-1-ol.

[0205] In a preferred embodiment, the at least one aroma chemical (i) is selected from the group consisting of methyl benzoate, benzyl acetate, geranyl acetate, 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, linalool, 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol and methyl benzoate.

[0206] In another preferred embodiment, the at least one aroma chemical (i) is selected from the group consisting of ethyl vanillin, vanillin, 2,5-dimethyl-4-hydroxy-2H-furan-3-one (furanone) and 3-hydroxy-2-methyl-4H-pyran-4-one (maltol).

[0207] Additional aroma chemicals with which compounds of the formula can be combined to obtain compositions according to the invention claimed herein can be found, for example, in S. Arctander, Perfume and Flavor Chemicals, Volumes I and II, Montclair, New Jersey, 1969, self-published or in H. Surburg and J. Panten, Common Fragrance and Flavor Materials, 4th edition, Wiley VCH Publishers, Weinheim 2016.In particular, mention may be made of: extracts from natural raw materials, such as essential oils, condensed fats, absolutes, resins, balms, tinctures, such as, for example, ambergris tincture; amyris oil; angelica seed oil; angelica root oil; anise seed oil; valerian oil; basil oil; moss absolute; laurel oil; artemisia oil; benzoin resin; bergamot oil; beeswax absolute; birch tar; bitter almond oil; savory oil; buchu leaf oil; kalua oil; juniper oil; calamus oil; camphor oil; ylang-ylang oil; cardamom oil; quinoa oil; cinnamon oil; cinnamon absolute; castoreum absolute; cedar leaf oil; cedarwood oil; labdanum oil; citronella oil; lemon oil; copaiba balsam; copaiba balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill leaf oil; dill seed oil; eau de toilette absolute; oakmoss absolute; elemi resin oil; tarragon oil; lemon eucalyptus oil; eucalyptus oil; anise oil; pine needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiac wood oil; guarana balsam; guarana balsam oil; helichrysum absolute; helichrysum oil; ginger oil; orris root absolute; orris root oil; jasmine absolute; calamus oil; blue chamomile oil; Roman chamomile oil; carrot seed oil; quinoa oil; pine needle oil; spearmint oil; caraway oil; lappa oil; lappa absolute; lappa tree ; Lavender absolute; Lavender oil; Lavender absolute; Lavender oil; Lemongrass oil; Lovage oil; Lime oil distilled; Lime oil pressed; Linalool oil; Litsea cubeba oil; Bay leaf oil; Nutmeg oil; Marjoram oil; Mandarin oil; Cinnamon bark oil; Mimosa absolute; Musk seed oil; Musk tincture; Clary sage oil; Nutmeg kernel oil; Myrrh absolute; Myrrh oil; Myrtle oil; Clove leaf oil; Clove flower oil; Neroli oil; Frankincense absolute; Frankincense oil; Red myrrh oil; Neroli absolute; Orange oil; Oregano oil; Palmarosa oil; Patchouli oil; Perilla oil; Peru balsam oil; Parsley leaf oil; Parsley seed oil; Orange leaf Oil; peppermint oil; pimento oil; pine oil; mint oil; rose absolute; rosewood oil; rose oil; rosemary oil; Dalmatian sage oil; Spanish sage oil; sandalwood oil; celery seed oil; lavender oil; anise oil; styrax oil; marigold oil; fir oil; tea tree oil; turpentine; thyme oil; tolu balsam; tonka bean absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniper berry oil; lees oil; wormwood oil; wintergreen oil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil, and their fractions, or components isolated therefrom;.

[0208] Individual fragrances from the group of hydrocarbons such as, for example, 3-carene; α-pinene; β-pinene; α-terpinene; γ-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; aurantium; (E,Z)-1,3,5-undecatriene; styrene; diphenylmethane;

[0209] Aliphatic alcohols such as, for example, hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol; 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)-3-hexenols; 1-octen-3-ol; a mixture of 3,4,5,6,6-pentamethyl-3 / 4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol;

[0210] Aliphatic aldehydes and acetals thereof, such as, for example, hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-9-undecenal; 2,6,10-trimethyl-5,9-undecadienal ; heptaldehyde diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyloxyacetaldehyde; (E / Z)-1-(1-methoxypropoxy)-hex-3-ene; aliphatic ketones and their oximes, such as, for example, 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; 6-methyl-5-hepten-2-one;

[0211] Aliphatic sulfur compounds, such as, for example, 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol;

[0212] Aliphatic nitriles, such as, for example, 2-nonenenitrile; 2-undecenenitrile; 2-tridecenenitrile; 3,12-tridecadienenitrile; 3,7-dimethyl-2,6-octadienenitrile; 3,7-dimethyl-6-octenenitrile;

[0213] Esters of aliphatic carboxylic acids, such as, for example, (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate Esters; (E)- and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octynoate; methyl 2-nonynoate; allyl 2-isopentyloxyacetate; methyl-3,7-dimethyl-2,6-octadienoate; 4-methyl-2-pentyl crotonate;

[0214] acyclic terpene alcohols, such as, for example, geraniol; nerol; linalool; lavandulol; nerolidol; farnesol; tetrahydrolinalool; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7-octatrien-1-ol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid esters and 3-methyl-2-butenoates;

[0215] acyclic terpene aldehydes and ketones, such as, for example, geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; and the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal; cyclic terpene alcohols, such as, for example, menthol; isopulegol; alpha-terpineol; terpinen-4-ol; menthane-8-ol; menthane-1-ol; menthane-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambroxanol; vetivol; guaiacol; and formates, acetates, propionates, isobutyrates, butyrates, isovalerates, valerates, hexanoates, crotonates, tiglic acid esters and 3-methyl-2-butenoate esters thereof;

[0216] Cyclic terpene aldehydes and ketones, such as, for example, menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; aniseed ketone; α-ionone; β-ionone; α-n-methylionone; β-n-methylionone; α-isomethylionone; β-isomethylionone; α-irone; α-damascone; β-damascone; β-damascone; δ-damascone; γ-damascone; 1-(2,4,4-trimethyl-2-cyclohexene)-1-yl)-1-yl-2-hydroxy-1-nitro-1-yl-2-nitro-1-nitro-1-nitro-1-nitro-1-nitro-1-nitro-1-nitro-1-nitro-1-nitro-1-nitro-1-nitro-1-nitro -1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-naphthone-8(5H)-one; 2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal; nootkatone; dihydronootkatone; 4,6,8-megatrien-3-one; α-sweet orange aldehyde; β-sweet orange aldehyde; acetylated cedarwood oil (methyl cedar ketone);

[0217] Cyclic alcohols, such as, for example, 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isobornylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;

[0218] Alicyclic alcohols, such as, for example, α-3,3-trimethylcyclohexylmethanol; 1-(4-isopropylcyclohexyl)ethanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-ol; -(2,2,3-trimethyl-3-cyclopent-1-yl)pentan-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol;

[0219] Cyclic and alicyclic ethers, such as, for example, eucalyptol; methyl cedarwood ether; cyclododecyl methyl ether; 1,1-dimethoxycyclododecane; (ethoxymethoxy)cyclododecane; α-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyldodecahydronaphtho[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo-[10.1.0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;

[0220] Cyclic ketones and macrocyclic ketones, such as, for example, 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecanone; 3-methyl-5-cyclopentadecanone; 3-methyl 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecene-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 8-cyclohexadecene-1-one; 7-cyclohexadecene-1-one; (7 / 8)-cyclohexadecene-1-one; 9-cycloheptadecene-1-one; cyclopentadecanone; cyclohexadecanone;

[0221] Cycloaliphatic aldehydes such as, for example, 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 2-methyl-4-(2,2,6-trimethylcyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarboxaldehyde;

[0222] Cycloaliphatic ketones such as, for example, 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 2,2-dimethyl-1-(2,4-dimethyl-3-cyclohexen-1-yl)-1-propanone; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthylmethyl ketone; methyl 2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl(2,4-dimethyl-3-cyclohexen-1-yl)ketone;

[0223] Esters of cyclic alcohols, such as, for example, 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-amylcyclohexyl acetate; 4-tert-amylcyclohexyl acetate; 3,3,5-trimethylcyclohexyl acetate; decahydro-2-naphthyl acetate; 2-cyclopentylcyclopentyl crotonate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate Esters; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl acetate; 4,7-methano-octahydro-5 or 6-indenyl acetate;

[0224] Esters of cycloaliphatic alcohols, such as, for example, 1-cyclohexylethyl crotonate;

[0225] Esters of cycloaliphatic carboxylic acids, such as, for example, allyl 3-cyclohexylpropionate; allyl cyclohexyloxyacetate; cis- and trans-methyl dihydrojasmonate; cis- and trans-methyl jasmonate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxolane-2-acetate;

[0226] Aromatic aliphatic alcohols, such as, for example, benzyl alcohol; 1-phenylethanol, 2-phenylethanol, 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethanol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxy-benzyl alcohol; 1-(4-isopropylphenyl)ethanol;

[0227] Esters of aromatic aliphatic alcohols and aliphatic carboxylic acids, such as, for example, benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethyl acetate; α-trichloromethylbenzyl acetate; α,α-dimethylphenylethyl acetate; α,α-dimethylphenylethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;

[0228] Aromatic aliphatic ethers, such as, for example, 2-phenylethyl methyl ether; 2-phenylethyl isopentyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydrogenated atroaldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxane; 4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxin; 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxin;

[0229] Aromatic and aromatic aliphatic aldehydes such as, for example, benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydroataldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 2-methyl-3-(4-isobutylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; meat Cinnamaldehyde; α-butylcinnamaldehyde; α-amylcinnamaldehyde; α-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylenedioxyphenyl)propanal;

[0230] Aromatic and araliphatic ketones such as, for example, acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthyl)-ethanone; 2-benzofuranylethanone; (3-methyl-2-benzofuranyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanylmethyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanylmethyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone; 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2'-naphthylacetophenone;

[0231] Aromatic and aliphatic carboxylic acids and their esters, such as, for example, benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isopentyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenylglycidate; ethyl 3-methyl-3-phenylglycidate;

[0232] Nitrogen-containing aromatic compounds, such as, for example, 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile; 3-methyl-5-phenyl-2-pentenenitrile; 3-methyl-5-phenylvaleronitrile; methyl anthranilate; methyl-N-methyl anthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarboxaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; 2-(3-phenylpropyl)pyridine; indole; skatole; 2-methoxy-3-isopropyl-pyrazine; 2-isobutyl-3-methoxypyrazine;

[0233] Phenols, phenyl ethers and phenyl esters, such as, for example, estragole; anethole; eugenol; eugenol methyl ether; isoeugenol; isoeugenol methyl ether; thymol; carvacrol; diphenyl ether; β-naphthyl methyl ether; β-naphthyl ethyl ether; β-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresyl phenyl acetate;

[0234] Heterocyclic compounds, such as, for example, 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;

[0235] Lactones, such as, for example, 1,4-octanolactone; 3-methyl-1,4-octanolactone; 1,4-nonanolactone; 1,4-decanolactone; 8-decene-1,4-lactone; 1,4-undecalactone; 1,4-dodecalactone; 1,5-decanolactone; 1,5-dodecalactone; 4-methyl-1,4-decanolactone; 1,15-pentadecalactone; cis- and trans-11-pentadecadecene-1,15-lactone; cis- and trans-1 2-Pentadecene-1,15-lactone; 1,16-hexadecene-1,16-lactone; 9-hexadecene-1,16-lactone; 10-oxa-1,16-hexadecene-lactone; 11-oxa-1,16-hexadecene-lactone; 12-oxa-1,16-hexadecene-lactone; 1,12-dodecanediolide ethylene ester; 1,13-tridecanediolide ethylene ester; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin; tetrahydroactinolide.

[0236] The aroma chemicals (X) used in the composition were obtained from known commercial sources and purchased from Germany.

[0237] In a preferred embodiment, the composition comprises at least one compound of formula (I) and at least one aroma chemical (X).

[0238] In another preferred embodiment, the composition comprises at least one compound of formula (Ia), at least one compound of formula (Ib) and at least one compound of formula (Ic) and at least one aromachemical (X).

[0239] Non-aromatic chemical carriers:

[0240] The non-fragrance chemical carrier in the composition of the present invention is preferably selected from the group consisting of surfactants, oil components, antioxidants, deodorant actives and solvents.

[0241] Preferably, at least one non-aromachemical carrier is a compound, a mixture of compounds or other additive which has no sensory properties or has no significant sensory properties. The non-aromachemical carrier may be used to dilute and / or immobilize the compound of formula (I) as defined above and - optionally at least one aromachemical (X) if included in the composition.

[0242] The non-aromatic chemical carrier in the composition of the present invention is preferably selected from the group consisting of a surfactant, an oil component, a solvent or any mixture of two or more of the foregoing.

[0243] Solvents

[0244] In the context of the invention claimed herein, a "solvent" is used to dilute the compound of formula (I) used according to the invention and does not have its own fragrance.

[0245] The amount of the one or more solvents is selected depending on the composition.

[0246] Preferably, the solvent is present in the composition in a total amount of 0.01 wt.% to 99.0 wt.%, more preferably in a total amount of 0.05 wt.% to 95.0 wt.%, still more preferably in a total amount of 0.1 wt.% to 80.0 wt.%, most preferably in a total amount of 0.1 wt.% to 70.0 wt.%, especially in a total amount of 0.1 wt.% to 60.0 wt.%, based on the total weight of the composition.

[0247] In a preferred embodiment, the composition comprises 0.05wt.% to 10wt.%, more preferably 0.1wt.% to 5wt.%, and even more preferably 0.2wt.% to 3wt.% of total solvent based on the total weight of the composition. In another preferred embodiment of the present invention, the composition comprises 20wt.% to 70wt.%, more preferably 25wt.% to 50wt.% of total solvent based on the total weight of the composition.

[0248] Preferred solvents are selected from the group consisting of ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, triethyl citrate, isopropyl myristate and any mixture of two or more of the foregoing.

[0249] In a preferred embodiment, the composition comprises at least one compound of formula (I) and at least one solvent and optionally at least one aroma chemical (X).

[0250] In another preferred embodiment, the composition comprises at least one compound of formula (Ia), at least one compound of formula (Ib), and at least one compound of formula (Ic) and at least one solvent and optionally at least one aroma chemical (X).

[0251] Oil component

[0252] Preferably, the total oil component is present in an amount of 0.1 wt.% to 80 wt.%, more preferably 0.5 wt.% to 70 wt.%, still more preferably 1 wt.% to 60 wt.%, even more preferably 1 wt.% to 50 wt.%, especially 1 wt.% to 40 wt.%, more especially 5 wt.% to 25 wt.% and specifically 5 wt.% to 15 wt.%, based on the total weight of the composition.

[0253] Preferably, the oil component is selected from Guerbet alcohols and other additional esters based on fatty alcohols containing 6 to 18, preferably 8 to 10, carbon atoms, such as myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, Stearyl erucate, isostearyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate, and erucyl erucate. Likewise suitable are esters of C18-C38-alkyl-hydroxycarboxylic acids with linear or branched C6-C22-fatty alcohols, more particularly dioctyl malate, esters of linear and / or branched fatty acids with polyols (e.g. propylene glycol, dimer diol or trimer triol), triglycerides based on C6-C10 fatty acids, liquid mono-, di- and triglyceride mixtures based on C6-C18 fatty acids, esters of C6-C22-fatty alcohols and / or Guerbet alcohols with aromatic carboxylic acids, more particularly benzoic acid, esters of dicarboxylic acids with polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22-fatty alcohol carbonates, such as, for example, dicaprylyl carbonate ( CC), Guerbet carbonates based on fatty alcohols containing 6 to 18, preferably 8 to 10, carbon atoms, esters of benzoic acid with linear and / or branched C6 to C22 alcohols (e.g. TN), a linear or branched, symmetrical or asymmetrical dialkyl ether having 6 to 22 carbon atoms in each alkyl group, such as dicaprylyl ether ( OE), ring-opening products of epoxidized fatty acid esters with polyols and hydrocarbons or mixtures thereof.

[0254] In a preferred embodiment, the composition comprises at least one compound of formula (I) and at least one oil component and optionally at least one aroma chemical (X).

[0255] In another preferred embodiment, the composition comprises at least one compound of formula (Ia), at least one compound of formula (Ib), and at least one compound of formula (Ic) and at least one oil component and optionally at least one fragrance chemical (X).

[0256] Antioxidants

[0257] It is understood that antioxidants are capable of inhibiting or preventing undesirable changes in the composition to be protected caused by the effects of oxygen and other oxidative processes. In most cases, the role of antioxidants is that they act as free radical scavengers of free radicals generated during auto-oxidation.

[0258] In a preferred embodiment, the antioxidant is selected from the group consisting of:

[0259] Amino acids (e.g. glycine, alanine, arginine, serine, threonine, histidine, tyrosine, tryptophan) and their derivatives,

[0260] Imidazoles (e.g. urocanic acid) and their derivatives,

[0261] Peptides, such as D,L-carnosine, D-carnosine, L-carnosine (=β-alanyl-L-histidine) and their derivatives,

[0262] Carotenoids, carotenes (e.g. α-carotene, β-carotene, lycopene, lutein) or their derivatives,

[0263] Chlorogenic acid and its derivatives,

[0264] Lipoic acid and its derivatives (e.g. dihydrolipoic acid),

[0265] aurothioglucose, propylthiouracil and other thiols (e.g. thioredoxin, glutathione, cysteine, cystine, cystamine and their glycosyl, N-acetyl, methyl, ethyl, propyl, pentyl, butyl and lauryl, palmitoyl, oleyl, gamma-linolenic acid, cholesteryl and glyceryl esters) and their salts,

[0266] Dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and its derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts),

[0267] Sulfoximine compounds (e.g., buthionine sulfoximine, homocysteine ​​sulfoximine, buthionine sulfone, pentyl-, hexyl-, heptylthionine sulfoximine),

[0268] · (Metal) chelators (e.g. alpha-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin),

[0269] · Alpha-hydroxy acids (e.g. citric acid, lactic acid, malic acid),

[0270] Humic acid, bile acid, bile extract, bilirubin, biliverdin, boldine (= alkaloids from the plant Boldine, Boldine extract,

[0271] EDTA, EGTA and their derivatives,

[0272] Unsaturated fatty acids and their derivatives (e.g. gamma-linolenic acid, linoleic acid, oleic acid),

[0273] Folic acid and its derivatives,

[0274] Ubiquinone and ubiquinol and their derivatives,

[0275] Vitamin C and derivatives (e.g. ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate),

[0276] Tocopherol and derivatives (e.g. vitamin E acetate),

[0277] Vitamin A and derivatives (e.g. vitamin A palmitate),

[0278] · Coniferyl benzoate of benzoin gum, rutin and its derivatives, α-glycosyl rutin, ferulic acid, furfurylidene glucitol,

[0279] Butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA),

[0280] · Nordihydroguaiaretic acid, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives,

[0281] Superoxide dismutase,

[0282] Zinc and its derivatives (such as ZnO, ZnSO4),

[0283] Selenium and its derivatives (e.g. selenomethionine),

[0284] Stilbene and its derivatives (e.g. stilbene oxide, trans-stilbene oxide)

[0285] and mixtures of two or more of the foregoing.

[0286] In a preferred embodiment, the antioxidant is selected from the group consisting of pentaerythritol, tetra-di-tert-butyl hydroxyhydrocinnamate, nordihydroguaiaretic acid, ferulic acid, resveratrol, propyl gallate, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), ascorbyl palmitate, tocopherol, and a mixture of two or more of the foregoing.

[0287] Preferably, the composition according to the invention claimed herein comprises antioxidants in a total amount of 0.001 wt.-% to 25 wt.-%, preferably 0.005 wt.-% to 10 wt.-%, more preferably 0.01 wt.-% to 8 wt.-%, still more preferably 0.025 wt.-% to 7 wt.-%, even more preferably 0.05 wt.-% to 5 wt.-%, based on the total weight of the composition.

[0288] In a preferred embodiment, the composition comprises at least one compound of formula (I) and at least one antioxidant and optionally at least one aroma chemical (X).

[0289] In another preferred embodiment, the composition comprises at least one compound of formula (Ia), at least one compound of formula (Ib), and at least one compound of formula (Ic), and at least one antioxidant and optionally at least one aroma chemical (X).

[0290] Deodorant active agent

[0291] Deodorizing compositions (deodorants and antiperspirants) counteract, mask or eliminate body odor. Body odor is formed by the action of skin bacteria on apocrine sweat, which leads to the formation of bad-smelling degradation products.

[0292] Preferably, the deodorant active is selected from the group consisting of antiperspirants, esterase inhibitors, antimicrobials and mixtures of two or more of the foregoing.

[0293] Suitable antiperspirants are selected from the group consisting of aluminum, zirconium or zinc. Examples are aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate and complex compounds thereof (e.g. with 1,2-propylene glycol), aluminum hydroxyallantoate, aluminum chlorotartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and complex compounds thereof (e.g. with amino acids such as glycine). Preferably aluminum chlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate and complex compounds thereof are used.

[0294] Preferably, the antiperspirant is selected from the group consisting of aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate, aluminum hydroxyallantoin, aluminum chlorotartrate, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate, and mixtures of two or more of the foregoing.

[0295] When sweat is present in the underarm area, extracellular enzymes - esterases, mainly proteases and / or lipases - are formed by bacteria and break down the esters present in the sweat, releasing the odor in the process. Suitable esterase inhibitors are, for example, trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate and in particular triethyl citrate. Esterase inhibitors inhibit the enzyme activity and thus reduce the odor formation. The free acid may be released by cleavage of the citrate esters and lower the pH of the skin to such an extent that the enzyme is inactivated by acylation. Other esterase inhibitors are sterol sulfates or phosphates, such as, for example, lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfates or phosphates, dicarboxylic acids and their esters, such as glutaric acid, monoethyl glutarate, diethyl glutarate, adipic acid, monoethyl adipate, diethyl adipate, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters, such as citric acid, malic acid, tartaric acid or diethyl tartrate, zinc glycinate and mixtures of two or more of the foregoing.

[0296] Preferably, the esterase inhibitor is selected from the group consisting of trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate, triethyl citrate, lanosterol, cholesterol, campesterol, stigmasterol, sitosterol sulfate, sitosterol phosphate, glutaric acid, monoethyl glutarate, diethyl glutarate, adipic acid, monoethyl adipate, diethyl adipate, malonic acid, diethyl malonate, citric acid, malic acid, tartaric acid, diethyl tartrate, zinc glycinate and a mixture of two or more of the foregoing.

[0297] Preferably, the composition according to the invention claimed herein comprises the esterase inhibitor in a total amount ranging from 0.01 to 20 wt.-%, preferably 0.1 to 10 wt.-% and more particularly 0.5 to 5 wt.-%, based on the total weight of the composition.

[0298] As used herein, the term "antimicrobial agent" encompasses substances with bactericidal and / or bacteriostatic properties. Typically, these substances act on Gram-positive bacteria, such as, for example, 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)-urea, 2,4,4'-trichloro-2'-hydroxydiphenyl ether (triclosan), 4-chloro-3,5-dimethylphenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 3-methyl-4-(1-methylethyl)-phenol, 2-benzyl -4-chlorophenol, 3-(4-chlorophenoxy)-propane-1,2-diol, 3-iodo-2-propynylbutyl carbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), phenoxyethanol, glyceryl monocaprate, glyceryl monocaprylate, glyceryl monolaurate (GML), diglyceryl monocaprate (DMC), salicylic acid-N-alkylamides such as, for example, salicylic acid-n-octylamide or salicylic acid-n-decylamide.

[0299] Preferably, the antimicrobial agent is selected from the group consisting of chitosan, phenoxyethanol, 5-chloro-2-(2,4-dichlorophenoxy)-phenol, 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl)-urea, 2,4,4'-trichloro-2'-hydroxydiphenyl ether (triclosan), 4-chloro-3,5-dimethylphenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 3-methyl-4 -(1-methylethyl)-phenol, 2-benzyl-4-chlorophenol, 3-(4-chlorophenoxy)-propane-1,2-diol, 3-iodo-2-propynylbutyl carbamate, chlorhexidine, 3,4,4'-trichlorocarbanilide (TTC), phenoxyethanol, glyceryl monocaprate, glyceryl monocaprylate, glyceryl monolaurate (GML), diglyceryl monocaprate (DMC), salicylic acid-N-alkylamide, and mixtures of two or more of the foregoing.

[0300] Preferably, the composition according to the herein claimed invention comprises one or more antimicrobial agents in a total amount ranging from 0.01 to 5 wt.% and preferably from 0.1 to 2 wt.-%, based on the total weight of the composition.

[0301] In a preferred embodiment, the composition comprises at least one compound of formula (I) and at least one deodorant active and optionally at least one fragrance chemical (X).

[0302] In another preferred embodiment, the composition comprises at least one compound of formula (Ia), at least one compound of formula (Ib), and at least one compound of formula (Ic) and at least one deodorant active and optionally at least one fragrance chemical (X).

[0303] Surfactants

[0304] Preferably, the surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures of two or more of the foregoing. More preferably, the surfactant is an anionic surfactant.

[0305] Preferably, the composition according to the invention contains one or more surfactants in a total amount of 0 to 40 wt.%, more preferably 0 to 20 wt.%, more preferably 0.1 wt.% to 15 wt.%, and especially 0.1 wt.% to 10 wt.%, based on the total weight of the composition.

[0306] Preferred nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers and mixed formals, optionally partially oxidized alkyl (alkenyl) oligoglycosides or glucuronic acid derivatives, fatty acid-N-alkyl glucamides, protein hydrolysates (especially wheat-based plant products), polyol fatty acid esters, sugar esters, sorbitan esters, polysorbates and amine oxides. If the nonionic surfactants contain polyglycol ether chains, they can have a conventional homolog distribution, but they preferably have a narrow range of homolog distribution.

[0307] Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one COO(-) or SO3(-) group in the molecule.

[0308] Particularly suitable zwitterionic surfactants are the so-called betaines, such as N-alkyl-N,N-dimethylammonium glycinates, for example, cocoalkyldimethylammonium glycinates, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example, cocoacylaminopropyldimethylammonium glycinates, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines, which contain 8 to 18 carbon atoms in the alkyl or acyl radical, and cocoacylaminoethylhydroxyethylcarboxymethylglycinate. Particular preference is given to the fatty acid amide derivatives known under the CTFA name of cocamidopropyl betaine.

[0309] Amphoteric surfactants are also suitable, particularly as cosurfactants. Amphoteric surfactants are surface-active compounds that contain at least one free amino group and at least one-COOH or-SO3H group in the molecule in addition to C8 to C18 alkyl or acyl groups and can form inner salts. Examples of suitable amphoteric surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyltaurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, which contain approximately 8 to 18 carbon atoms in the alkyl group. Particularly preferred amphoteric surfactants are N-coconut alkylaminopropionate, cocoylaminoethylaminopropionate and acylsarcosine.

[0310] Anionic surfactants are characterized by a water-soluble anionic group (such as, for example, a carboxylate, sulfate, sulfonate or phosphate group) and a lipophilic group. Dermatologically safe anionic surfactants are known to many practitioners from relevant textbooks and are commercially available. They are in particular alkyl sulfates, alkyl ether sulfates, alkyl ether carboxylates, acyl isethionates, acyl sarcosinates, acyl taurines and sulfosuccinates containing linear C12-C18 alkyl or acyl groups and acyl glutamates in the form of their alkali metal, ammonium or alkanolammonium salts.

[0311] Particularly suitable cationic surfactants are quaternary ammonium compounds, preferably ammonium halides, more particularly chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. In addition, readily biodegradable quaternary ester compounds, for example dialkylammonium methylsulfates and methylhydroxyalkyldialkyloxyalkylammonium methylsulfates, as sold under the name Stepantexe, and the corresponding The products of the series of quaternary ammonium salts can be used as cationic surfactants. "Esterquats" are generally understood to be quaternary fatty acid triethanolamine ester salts. They can provide a specific softness to the composition. They are known substances prepared by relevant methods of organic chemistry. Other cationic surfactants suitable for use according to the invention are quaternary protein hydrolysates.

[0312] Due to the characteristic sensory properties of compounds of formula (I) and their firmness, persistence and stability, it can be used in particular to provide an odor, preferably a fragrance effect, to surfactant-containing compositions, such as, for example, detergents (especially laundry care products and multi-purpose cleaners). It can preferably be used to impart a persistent woody, fruity, herbal, green, root, citrus, petitgrain, floral, damascena, tobacco, ashtray, gourmet, sweet, ionone, ambergris, fresh, natural, fir needle, camphor, vanilla root to compositions containing surfactants.

[0313] In a preferred embodiment, the composition comprises at least one compound of formula (I) and at least one surfactant and optionally at least one fragrance chemical (X).

[0314] In another preferred embodiment, the composition comprises at least one compound of formula (Ia), at least one compound of formula (Ib), and at least one compound of formula (Ic) and at least one surfactant and optionally at least one fragrance chemical (X).

[0315] Suitable compositions are, for example, perfume compositions, body care compositions (including cosmetic compositions and products for oral and dental hygiene), hygiene preparations, cleaning compositions (including dishwashing compositions), textile detergent compositions, compositions for fragrance dispensers, foods, food supplements, pharmaceutical compositions and crop protection compositions.

[0316] The perfume composition may be chosen from fine perfumes, air fresheners in liquid form, in gel-like form or in the form of an application to a solid carrier, aerosol sprays, scented cleansers, scented candles and oils, such as lamp oils or oils for massage.

[0317] Examples of fine fragrances are perfume extracts, eau de parfums, eau de toilettes, colognes, solid perfumes and parfums.

[0318] Body care compositions include cosmetic compositions and products for oral and dental hygiene and can be chosen from aftershaves, preshave products, splash colognes, solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions of the oil-in-water, water-in-oil and water-in-oil-in-water types, such as, for example, skin creams and lotions, face creams and lotions, sunscreen creams and lotions, aftersun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products, such as, for example, hair sprays, hair gels, hair styling lotions, hair conditioners , shampoos, permanent and semi-permanent hair colorants, hair styling compositions, such as cold wave and hair smoothing compositions, hair tonics, hair creams and hair lotions, deodorants and antiperspirants, such as underarm sprays, roll-ons, deodorant sticks and deodorant creams; decorative cosmetic products, such as eyeliners, eye shadows, nail polishes, foundations, lipsticks and mascaras; and products for oral and dental hygiene, such as toothpastes, dental floss, mouthwashes, breath fresheners, dental foams, dental gels and dental strips.

[0319] The hygiene article may be selected from scented sticks, insecticides, insect repellents, propellants, rust removers, fragrance freshening wipes, underarm pads, baby diapers, sanitary napkins, toilet paper, cosmetic wipes, handkerchiefs, dishwashing detergents and deodorants.

[0320] Cleaning compositions, such as, for example, cleaners for solid surfaces, can be chosen from aromatic acidic, alkaline and neutral cleaners, such as, for example, floor cleaners, window cleaners, dishwashing compositions for both hand and machine washing purposes, bath and sanitary cleaners, scouring creams, solid and liquid toilet cleaners, powder and foam carpet cleaners, waxes and polishes, such as furniture polishes, floor waxes, shoe polishes, disinfectants, surface disinfectants and sanitary cleaners, brake cleaners, pipe cleaners, limescale removers, grill and oven cleaners, algae and moss removers, mildew removers, facade cleaners.

[0321] The textile detergent composition may be selected from liquid detergents, powder detergents, laundry pretreaters (such as bleaches, soaking agents and stain removers), fabric softeners, detergent soaps, detergent tablets.

[0322] Food means raw, cooked, or processed edible substances, ices, beverages, or ingredients, or chewing gums, soft candies, jellies, and candies, used or intended for use, in whole or in part, for human consumption.

[0323] A dietary supplement is a product intended for ingestion that contains dietary ingredients intended to add additional nutritional value to the diet. A dietary ingredient may be one or any combination of the following: a vitamin, a mineral, an herb or other botanical, an amino acid, a dietary substance, a concentrate, a metabolite, a component, or an extract that a person uses to supplement their diet by increasing their total dietary intake. A dietary supplement may be found in a variety of forms such as tablets, capsules, soft gels, softgels, liquids, or powders.

[0324] Pharmaceutical compositions include compositions intended for use in the diagnosis, cure, mitigation, treatment, or prevention of disease, as well as preparations (other than foods) intended to affect the structure or any function of the body of man or other animals.

[0325] Crop protection compositions include compositions intended for the management of plant diseases, weeds and other harmful organisms (both vertebrates and invertebrates) that damage agricultural crops and forestry.

[0326] Preferably, the composition according to the invention further comprises at least one auxiliary agent selected from the group consisting of preservatives, abrasives, anti-acne agents, anti-skin aging agents, anti-cellulite agents, anti-dandruff agents, anti-inflammatory agents, anti-irritants, irritation reducing agents, astringents, antiperspirants, bactericides, antistatic agents, adhesives, buffers, carrier materials, chelating agents, cell stimulants, care agents, depilatories, emulsifiers, enzymes, essential oils, fibers, film formers, fixatives, foam formers, foam stabilizers, substances that prevent foaming, foam boosters, fungicides, gelling agents, gel formers, hair care agents, hair fixatives, hair smootheners, water enhancers, moisturizing substances, wetting substances, bleaching agents, enhancers, detergents, optical Brighteners, impregnants, stain repellents, friction reducers, lubricants, moisturizers, ointments, sunscreens, plasticizers, covering agents, polishes, luminizers, polymers, powders, proteins, refatting agents, exfoliants, silicones, skin soothing agents, skin cleansers, skin care agents, skin healing agents, skin brighteners, skin protectants, skin softeners, cooling agents, skin cooling agents, warming agents, skin warming agents, stabilizers, UV absorbers, UV filters, fabric softeners, suspending agents, skin tanning agents, thickeners, vitamins, waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, alpha-hydroxy acids, polyhydroxy fatty acids, liquefiers, dyes, color protectants, pigments, corrosion inhibitors, polyols, electrolytes and silicone derivatives.

[0327] The invention relates to the preparation of a composition and a method for imparting a fragrance effect to the composition.

[0328] One embodiment of the present invention relates to a method for preparing a composition of a compound of formula (I), the composition comprising:

[0329] (i) at least one aroma chemical (X) other than a compound according to the invention or

[0330] (ii) at least one non-aroma chemical carrier, or

[0331] Both (i) and (ii).

[0332] The present invention also relates to a method for enhancing the fragrance effect of a composition, wherein the method comprises incorporating at least one compound having formula (I) into the composition.

[0333] In particular, the present invention relates to a method for preparing a perfume composition, a body care composition, a hygiene article, a cleaning composition, a textile detergent composition, a composition for a fragrance dispenser, a food, a food supplement, a pharmaceutical composition or a crop protection composition, which comprises making the perfume composition, the body care composition, the hygiene article, the cleaning composition, the textile detergent composition, the composition for a fragrance dispenser, the food, the food supplement, the pharmaceutical composition or the crop protection composition contain at least one compound of formula (I).

[0334] In one embodiment, the present invention relates to a method for imparting a fragrance note reminiscent of woody notes, fruity notes, herbal notes, green notes, root notes, citrus notes, petitgrain notes, floral notes, damascena notes, tobacco notes, ashtray notes, gourmet notes, sweet notes, vanilla root notes, ionone notes, ambergris notes, fresh notes, natural notes, fir needle notes, camphor notes to a perfume composition, a body care composition, a hygiene article, a cleaning composition, a textile detergent composition, a composition for a fragrance dispenser, a food, a food supplement, a pharmaceutical composition or a crop protection composition, comprising comprising at least one compound having formula (I) in the perfume composition, the body care composition, the hygiene article, the cleaning composition, the textile detergent composition, the composition for a fragrance dispenser, the food, the food supplement, the pharmaceutical composition or the crop protection composition.

[0335] quantity

[0336] In general, the total amount of compounds of formula (I) in the compositions, methods and uses according to the invention is typically adapted to the particular intended use or intended application and can therefore vary within wide ranges. In general, conventional standard commercial amounts for aroma chemicals, preferably for fragrances, are used.

[0337] Preferably, the composition according to the invention comprises compounds of formula (I) in a total amount of 0.001 wt.% to 99.9 wt.%, based on the total weight of the composition.

[0338] In particular, the composition comprises compounds of formula (I) in a total amount of 0.001 wt.% to 99.5 wt.%, preferably 50 wt.% to 99 wt.%, more preferably 80 wt.% to 95 wt.% and especially 90 wt.% to 95 wt.%, based on the total weight of the composition.

[0339] In particular, the composition comprises compounds of formula (I) in a total amount of 0.005 wt.% to 80 wt.%, preferably 0.1 wt.% to 30 wt.%, more preferably 1 wt.% to 20 wt.%, and especially 5 wt.% to 15 wt.%, based on the total weight of the composition.

[0340] In particular, the composition comprises compounds of formula (I) in a total amount of 0.001 wt.% to 20 wt.%, preferably 0.005 wt.% to 6 wt.%, more preferably 0.05 wt.% to 4 wt.%, and especially 0.1 wt.% to 3 wt.%, based on the total weight of the composition.

[0341] The terms compound (I) and compound having formula (I) are used interchangeably throughout the specification. In addition, the terms various compounds (I) and various compounds having formula (I) are used interchangeably throughout the specification.

[0342] Example

[0343] Hereinafter, a list of examples is provided to further illustrate the present disclosure without intending to limit the present disclosure to the specific examples listed below.

[0344] 1. At least one compound having formula (I)

[0345]

[0346] or a stereoisomer thereof for imparting a fragrance effect to a composition,

[0347] in,

[0348] X1 and X3 together form a double bond between the carbon atoms to which they are bonded, provided that X2 and X4 are hydrogen; or

[0349] X3 and X4 together form a double bond between the carbon atoms to which they are bonded, provided that X1 and X2 are hydrogen; or

[0350] X2 and X3 together form a double bond between the carbon atoms to which they are bonded, provided that X1 and X4 are hydrogen; or

[0351] X4 is OH, X1, X2 and X3 are all hydrogen,

[0352] Wherein R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0353] 2. The use according to embodiment 1, wherein the compound of formula (I) comprises at least one compound of formula (Ia)

[0354]

[0355] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0356] or at least one compound of formula (Ib),

[0357]

[0358] or at least one compound of formula (Ic),

[0359]

[0360] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0361] or at least one compound of formula (Id),

[0362]

[0363] or a stereoisomer thereof or a mixture of stereoisomers thereof,

[0364] or a mixture thereof;

[0365] in,

[0366] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0367] 3. The use of any one of embodiments 1 to 2, wherein R is selected from methyl, ethyl, propyl, butyl, isobutyl, isopropyl, 1-propenyl, or 2-propenyl.

[0368] 4. The use according to any one of embodiments 1 to 3, wherein R is selected from methyl, ethyl or 1-propenyl.

[0369] 5. Use of the mixture according to embodiments 2 to 4, wherein the weight ratio of the at least one compound of formula (Ia) to the at least one compound of formula (Ib) is in the range of 0.1:99.9 to 99.9:0.1.

[0370] 6. Use of a mixture according to any one of embodiments 2 to 5, wherein the weight ratio of the at least one compound of formula (Ia) to the at least one compound of formula (Ib) is in the range of 20:80 to 80:20, preferably 30:70 to 70:30 or preferably 40:60 to 60:40 or is preferably 50:50.

[0371] 7. The use of a mixture according to any one of embodiments 2 to 6, wherein the mixture has a ratio in the range of 90:10 to 99.9:0.1, wherein the ratio represents the combined amount of the compound of formula (Ia) and the compound of formula (Ib) to the compound of formula (Ic).

[0372] 8. A method of imparting a fragrance effect to a composition, the method comprising at least the step of adding a compound of formula (I) according to any one of Embodiments 1 to 7 to the composition.

[0373] 9. The use or method of any one of embodiments 1 to 8, wherein the aromatic effect is selected from the group consisting of woody notes, fruity notes, herbal notes, green notes, root notes, citrus notes, petitgrain notes, floral notes, damascena notes, tobacco notes, ashtray notes, gourmet notes, sweet notes, vanilla root notes, ionone notes, ambergris notes, fresh notes, natural notes, fir needle notes, camphor notes, or any combination of two or more of these notes.

[0374] 10. The use or method of any one of embodiments 1 to 8, wherein the at least one compound of formula (I) is used in a total amount ranging from ≥ 0.001 wt.% to ≤ 70.0 wt.%, based on the total weight of the composition.

[0375] 11. A composition comprising:

[0376] i) at least one compound of formula (I) according to any one of Embodiments 1 to 7, and

[0377] ii) at least one aroma chemical (X) other than a compound of formula (I), or

[0378] iii) at least one non-aroma chemical carrier, or

[0379] iv) Both (ii) and (iii).

[0380] 12. The composition of embodiment 11, wherein the at least one compound of any one of embodiments 1 to 7 is present in a range of ≥ 0.01 wt. % to ≤ 70.0 wt. %, based on the total weight of the composition.

[0381] 13. The composition of embodiment 11, wherein the at least one non-fragrance chemical carrier (ii) is selected from a surfactant, an oil component, an antioxidant, a deodorant active, or a solvent.

[0382] 14. The composition of any of embodiments 11 to 13, wherein the composition is selected from a perfume composition, a body care composition, a hygiene article, a cleaning composition, a textile detergent composition, a composition for a fragrance dispenser, a food, a food supplement, a pharmaceutical composition, or a crop protection composition.

[0383] 15. A mixture comprising at least one compound of formula (Ib),

[0384]

[0385] and

[0386] At least one compound having formula (IV)

[0387]

[0388] or a stereoisomer thereof or a mixture of stereoisomers thereof, wherein

[0389] R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

[0390] 16. Use of the mixture according to embodiment 15 for imparting a fragrance effect to a composition.

[0391] 17. A method of imparting a fragrance effect to a composition, the method comprising at least the step of adding the mixture according to embodiment 15 to the composition.

[0392] 18. The mixture, or the use, or the method according to any one of embodiments 15 to 17, wherein the weight ratio of the compound of formula (Ib) to the compound of formula (IV) is in the range of 90:10 to 99:1.

[0393] 19. The use or method of any one of embodiments 16 to 18, wherein the fragrance effect is selected from leather or plastic or a combination thereof.

[0394] 20. A method for preparing a mixture of at least one compound of formula (I) according to any one of embodiments 1 to 7, the method comprising at least the following steps

[0395] a) cyclizing a compound of formula (III) using a catalytic amount of an acid,

[0396]

[0397] wherein R is selected from C1-C5 straight chain or branched alkyl and C3-C5 straight chain or branched alkenyl,

[0398] to produce the at least one compound of formula (I),

[0399] b) optionally purifying the at least one compound of formula (I).

[0400] Examples:

[0401] The invention is illustrated in detail by the non-limiting working examples hereinafter. More particularly, the test methods specified hereinafter are part of the general disclosure of the present application and are not limited to the specific working examples.

[0402] 1. Analytical methods and materials:

[0403] Material:

[0404] Chemicals:

[0405] Chemicals were purchased from commercial suppliers (ABCR, Acros Organics, Alfa Aesar, Apollo Scientific, Fluorochem, Manchester Organics, Sigma-Aldrich, TCI) and used without further purification unless otherwise noted.

[0406] Analytical methods:

[0407] NMR Spectroscopy:

[0408] pass 13 C NMR and 1 H NMR characterization. 13 C NMR and 1 H NMR spectra were measured on a Bruker AV-500 spectrometer.

[0409] (Flash) column chromatography

[0410] (Flash) column chromatography was performed using silica gel (Merck) 230-400 mesh, particle size: 43-63 μm) or with distilled technical grade solvents. The solvent mixture and volume ratio (v / v) used as mobile phase for chromatography are specified in the corresponding experiments. Flash column chromatography is carried out in a glass column by applying a slightly elevated air or argon (0.3 mbar) pressure.

[0411] Gas chromatography (GC)

[0412] Gas chromatography (GC) was performed on an HP 6890 and 5890 series instrument equipped with a split mode capillary injection system and a flame ionization detector (FID) using hydrogen (H2) as the carrier gas.

[0413] 2. Synthesis

[0414] Example 1: Preparation of α-cyclohomogeranic acid methyl ester (α-1), β-cyclohomogeranic acid methyl ester (β-1), and γ-cyclohomogeranic acid methyl ester (γ-1)

[0415]

[0416] In a 250 ml reactor (equipped with a flow blocker, an impeller stirrer, a condenser and an Ar-inert gas connection), homogeranic acid methyl ester (53 g, 97.65% of the sum of E / Z-isomers, 0.264 mol) was dissolved in toluene (120 ml) and heated to 100° C. The solution was stirred vigorously and a catalytic amount of H PO (85%, 4.4 g) was added by syringe. The reaction mixture was stirred at 100° C. for 2 h. Reaction control by gas chromatography indicated that homogeranic acid methyl ester was completely converted. The reaction mixture was cooled to room temperature and quenched with a saturated Na CO solution (250 ml). The organic layer was separated from the aqueous layer and the aqueous layer was extracted twice with 100 ml of methyl tert-butyl ether (MTBE). The combined organic phases were dried over Na SO , filtered, and the solvent was removed by a rotary evaporator under vacuum (100-10 mbar) at 40° C.-50° C. After removal of the solvent, 52 g of a light yellow residue were obtained with the following product distribution determined by GC: 36.3% α-cyclohomogeranic acid methyl ester (α-1), 35.7% β-cyclohomogeranic acid methyl ester (β-1), 2.9% γ-cyclohomogeranic acid methyl ester (γ-1).

[0417] 44 g of the crude product were purified in a fractionated batch distillation (concentric column, 60 plates) at a pressure of 1 mbar, a tank temperature of 90° C. to 112° C. and a reflux ratio of 50: 1. The contents and purities of the various fractions are summarized in Table 1.

[0418] Table 1. Fractionation of methyl cyclohomogeranate (1)

[0419]

[0420]

[0421] Distillation fractions were used to obtain the aroma samples in Table 2.

[0422] Table 2 Composition of fractions (enriched isomers) selected for olfactory evaluation according to Example 1

[0423]

[0424] Example 2: Preparation of α-cyclic homogeranic acid ethyl ester (α-2), β-cyclic homogeranic acid ethyl ester (β-2), and γ-cyclic homogeranic acid ethyl ester (γ-2)

[0425]

[0426] In a 500 ml reactor (equipped with a baffle, an impeller stirrer, a condenser and an Ar-inert gas connection), the starting material homogeranic acid ethyl ester (120 g, 97.5% of the sum of E / Z-isomers, 0.264 mol) was dissolved in toluene (350 ml) and heated to 100° C. The solution was stirred vigorously and a catalytic amount of H PO (85%, 10.2 g) was added by syringe. The reaction mixture was stirred at 100° C. for 4 h. Reaction control by gas chromatography indicated a conversion of homogeranic acid ethyl ester>90%. The reaction mixture was cooled to room temperature and quenched with a saturated Na CO solution (400 ml). The organic layer was separated from the aqueous layer and the aqueous layer was extracted twice with 250 ml of methyl tert-butyl ether (MTBE). The combined organic phases were dried over Na SO , filtered, and the solvent was removed by a rotary evaporator under vacuum (100-10 mbar) at 40° C.-50° C. After removal of the solvent, 114 g of a pale yellow residue were obtained with the following product content: GC analysis α-2+β-2+γ-2=68.9% (isomers were not separated by GC).

[0427] 114 g of the crude product were purified in a fractionated batch distillation (concentric column, 60 plates) at a pressure of 1 mbar, a tank temperature of 90° C. to 93° C. and a reflux ratio of 50: 1. The contents and purities of the various fractions are summarized in Table 3.

[0428] Table 3. Fractionation of ethyl cyclohomogeranate (2)

[0429]

[0430] Analysis by NMR indicated only minor separation of isomers. Therefore, the following fractions were unified into three aroma samples - see Table 4.

[0431] NMR analysis of FR.4-8

[0432] α / β-Cyclohomogeranic acid ethyl ester (α / β-2)

[0433] The NMR data of the distillation fraction FR.4-8 showed that the ratio α-2:β-2=45:55

[0434] 13C NMR(CDCl3,126MHz)δ(ppm)174.4,172.8,135.2,131.3,130.5,121.35,60.4,60.3,45.6,39.3, 35.9,34.7,33.8,32.7,32.2,31.3,28.1,27.9,26.9,26.2,22.9,22.7,20.3,19.4,14.2,14.2.

[0435] Table 4. Composition of fractions (enriched isomers) selected for olfactory evaluation according to Example 2

[0436]

[0437] Example 3: Preparation of α-cyclic homogeranic acid methyl ester (α-1), β-cyclic homogeranic acid methyl ester (β-1), and γ-cyclic homogeranic acid methyl ester (γ-1).

[0438] Into 100mL round-bottomed flask, load (E / Z)-homogeranic acid methyl ester (3.92g, 20mmol) and the magnetic stirring bar of PTFE coating.Starting material is dissolved in hexafluoroisopropanol (20mL, 9.5 equivalents, 1M), and TFA (trifluoroacetic acid, 2.38g, 20.9mmol) is dripped in the solution stirred (after adding TFA in 1min, observe color immediately from colorless through bright yellow, then bright orange becomes dark orange red), and gained red solution is stirred for 24h at 25 DEG C.After this time, the dark brown-red reaction mixture is concentrated under reduced pressure.Residue is dissolved in hexane / MTBE (19:1v / v, 20mL), diatomite is added and slurries are concentrated under reduced pressure. Purification was performed by flash column chromatography on silica gel (Merck, 40-63 μm, 300 g, d×l=6×22 cm) using hexane / MTBE (gradient elution: hexane / MTBE=19:1 to 4:1 v / v) as eluent, followed by drying overnight in vacuo to afford methyl cyclohomogeranate (2.34 g, 11.9 mmol, 60% yield, based on GC, α-1:β-1:γ-1=31:68:1) as a colorless oil. The purified isomer mixture was used as a flavor sample (Table 5).

[0439] Table 5 Composition of fractions (enriched isomers) selected for olfactory evaluation according to Example 3

[0440]

[0441] Example 4: Preparation of γ-cyclohomogeranic acid methyl ester (γ-1)

[0442]

[0443] Under argon, 50mL Schlenk tubes equipped with a PTFE-coated magnetic stirring bar were charged with methyltriphenylphosphonium bromide (3.60g, 10.1mmol) and potassium tert-butoxide (1.1g, 9.80mmol). Anhydrous THF (25mL) was added, the Schlenk tube was immersed in a preheated oil bath at 50°C, and the resulting bright yellow suspension was heated at this temperature for 2h. Thereafter, the yellow reaction mixture was cooled to 0°C, and a solution of 2-(2,2-dimethyl-6-oxocyclohexyl) methyl acetate (0.98g, 4.97mmol) in anhydrous THF (7mL) was added dropwise. After the addition was complete, the resulting orange-brown reaction mixture was stirred at room temperature for 2.5h. After this time, the reaction mixture was treated with water (50mL) and brine (50mL), and the aqueous phase was extracted with ether (3×50mL). The organic layer combined is through Na2SO4 drying, filtered, and concentrated under reduced pressure, to provide the crude product as yellow oil.Use hexane / MTBE (gradient elution: hexane / MTBE 39:1 to 19:1v / v) as eluent to purify by flash column chromatography on silica gel to obtain (±)-γ-ring homogeranic acid methyl ester (γ-1) (753mg, 3.84mmol, 77% yield) as colorless oil.

[0444] γ-Cyclohomogeranic acid methyl ester (γ-1)

[0445] 1 H NMR (CDCl3, 501MHz) δ (ppm) = 4.75 (q, J = 1.4Hz, 1H), 4.56 (s, 1H), 3.64 (s, 3H), 2.50 (t, J = 10.2Hz, 1H), 2.46–2.38 (m, 2H), 2.22 (dt, J = 12.7, 6.1 Hz,1H),2.05(ddd,J=13.1,8.2,5.3Hz,1H),1.43(ddd,J=11.6,7.2,4.3Hz,1H),1.35(ddd,J=13.3,8.1,4.9Hz,1H),0.96(s,3H),0.79(s,3H).

[0446] GC DB-Waxetr 0.25 mm / 0.25 mm, 30 m, temperature: 220 °C (injector) / 60 °C to 135 °C at 2 °C / min, then 6 °C / min to 220 °C, then 12 °C / min to 260 °C, then 5 min at 260 °C, 350 °C (detector), gas: 0.60 bar H2, sample volume: 0.2 μL, t R =29.71min (99%).

[0447] The aroma effect of the thus obtained γ-cyclohomogeranic acid methyl ester (γ-1) was evaluated and designated as sample S8.

[0448] Example 5: Preparation of β-cyclohomogeranic acid methyl ester (β-1)

[0449]

[0450] Under argon atmosphere, sodium hydroxide (powder; 1.53 g, 38.3 mmol, 2.5 eq) was transferred to a 50 mL round bottom flask equipped with a PTFE coated magnetic stir bar. Methanol and MTBE (15 mL each) were added, and the resulting colorless suspension was stirred until the sodium hydroxide was almost completely dissolved. The methyl ester (mixture of α-1 / β-1 / γ-1; 3.00 g, 15.3 mmol, 1.0 eq) was added via syringe, and the resulting pale yellow solution was stirred at room temperature overnight. After this time, the crude reaction mixture was 1 H NMR analysis indicated that the approximate ratio of α-1:β-1 of the remaining cyclohomogeranic acid methyl ester was 25:75. After heating to 50°C for 3 h, 1 H NMR analysis indicated an approximate ratio of α-1:β-1 of the remaining cyclohomogeranic acid methyl ester of 10:90. The reaction mixture was concentrated under reduced pressure and diluted with water (20 mL) and MTBE (20 mL). The two-phase mixture was poured into ice-cold 10% aqueous hydrochloric acid solution (15 mL) and water (20 mL). The phases were separated and the aqueous phase was extracted with MTBE (3×50 mL). The combined organic layers were washed with brine (50 mL), dried over Na2SO4, filtered and concentrated under reduced pressure. The crude reaction mixture was purified by HPLC. 1 H NMR analysis indicated α-1:β-1=3:97. The ratio between β-1 and β-cyclohomogeranic acid was 54:46. The crude reaction mixture was purified by flash column chromatography on silica gel (200 g, d×l=6×15 cm) eluted with hexane / MTBE (19:1 v / v) to give β-1 (799 mg, 4.07 mmol, 27% yield) as a colorless oil. Further elution with hexane / ethyl acetate (gradient elution: 4:1 to 2:1 v / v) gave a mixture of α-cyclohomogeranic acid and β-cyclohomogeranic acid as a colorless solid (1.43 g, 7.82 mmol, 51% yield).

[0451] β-Cyclohomogeranic acid methyl ester (β-1)

[0452] 1H NMR (CDCl3, 501MHz) δ (ppm) = 3.66 (s, 3H), 3.05 (s, 2H), 2.01–1.96 (m, 2H), 1.65–1.54 (m, 2H), 1.58 (s, 3H), 1.48–1.44 (m, 2H), 0.96 (s, 6H).

[0453] 13 C NMR (CDCl3, 126MHz) δ (ppm) = 173.5, 131.6, 130.5, 51.8, 39.5, 34.9, 33.7, 32.8, 28.1, 20.4, 19.5.

[0454] GC DB-Waxetr 0.25 mm / 0.25 mm, 30 m, temperature: 220 °C (injector) / 60 °C to 135 °C at 2 °C / min, then 6 °C / min to 220 °C, then 12 °C / min to 260 °C, then 5 min at 260 °C, 350 °C (detector), gas: 0.60 bar H2, sample volume: 0.2 μL, t R =29.0min(GC-MS:m / z[M] + =196).

[0455] HRMS (GC-EI) m / z C 12 H 20 O2 + [M] + Calculated value: 196.1458; measured value: 196.1457.

[0456] The aroma effect of the β-cyclohomogeranic acid methyl ester (β-1) thus obtained was evaluated and designated as sample S10.

[0457] Example 6: Preparation of (E)-methyl 2-(2,2,6-trimethylcyclohexylidene)acetate (3 / compound of formula (IV))

[0458]

[0459] Diisopropylamine (3.25g, 32.1mmol, 1.7 equivalents) is transferred to a flame-dried 250mL round-bottom flask equipped with a PTFE-coated magnetic stirring bar and equipped with an argon outlet and a rubber septum. Anhydrous THF (30mL) is added and the colorless solution is cooled to -78 ° C. Then, n-butyl lithium (2.5M solution in n-hexane, 12mL, 30mmol, 1.6 equivalents) is added, and the resulting bright yellow solution is stirred for 15min at -78 ° C. Then anhydrous methyl acetate (2.05g, 27.6mmol, 1.5 equivalents) is added dropwise. After completion of the addition, stirring is continued for 30min. Then, at -78 ° C, a solution of 2,6,6-trimethylcyclohexanone (2.62g, 18.7mmol, 1.0 equivalents) in anhydrous THF (10mL, flask is rinsed with 2×5mL THF) is added dropwise. After the addition is complete, the reaction mixture is stirred for another 3h at this temperature. Then, saturated NH4Cl aqueous solution (50mL) is added, and the reaction mixture is diluted with MTBE (20mL) and water (50mL). The organic phase is separated and the aqueous phase is extracted with MTBE (3×50mL). The combined organic layer is washed with brine (50mL), dried over Na2SO4, filtered and concentrated under reduced pressure to obtain a crude product (4.00g, 18.7mmol, 4:epi-4=86:14 diastereoisomer mixture) as a light yellow oil. The crude β-hydroxy ester is directly used in the next step without further purification. At 0°C, distilled phosphoryl chloride (2.6mL, 4.30g, 28.0mmol, 1.5 equivalents) is added to a solution of β-hydroxy ester in anhydrous pyridine (20mL), and the resulting colorless solution is stirred at room temperature for 30min. Then, reaction vessel is immersed in the preheated oil bath at 100 ℃ and reaction mixture is stirred at this temperature for 18h.After cooling to room temperature, dark brown reaction mixture is quenched with ice-cold water (50mL), diluted with MTBE (50mL) and filtered through a small silica gel pad into a separatory funnel containing 100mL 5% aqueous HCl.Separate each phase and extract with MTBE (3 × 100mL) for aqueous phase.The organic layer merged is washed with 1M HCl (150mL) and saline (150mL), through Na2SO4 drying, filtered and concentrated under reduced pressure, to obtain the crude product as yellow oil.Use hexane / MTBE (gradient elution: hexane / MTBE 39:1 to 19:1v / v) as eluent on silica gel by flash column chromatography to purify, obtain the title compound as colorless oil.In addition to α-1 (168 mg, 0.86 mmol, 4.6% yield), β-1 (1.91 g, 9.73 mmol, 52% yield) and γ-1 (71.3 mg, 0.36 mmol, 1.9% yield), (E)-2-(2,2,6-trimethylcyclohexylidene)-acetic acid methyl ester 3 (272 mg, 1.38 mmol, 7.4% yield) was obtained, which corresponds to a total yield of 66% from 2,2,6-trimethylcyclohexanone over two steps. The NMR data of methyl cyclohomogeranate isomers are based on literature data.

[0460] (E)-2-(2,2,6-Trimethylcyclohexylidene)acetic acid methyl ester (3)

[0461] 1 H NMR (CD2Cl2, 501MHz) δ (ppm) = 5.75 (s, 1H), 4.02–3.89 (m, 1H), 3.64 (s, 3H), 1.82 (qt, J = 12.7, 3.5Hz, 1H), 1.62– 1.50(m,3H),1.49–1.42(m,1H),1.39(td,J=12.8,4.1Hz,1H),1.22(d,J=7.5Hz,3H),1.16(s,3H),1.11(s,3H).

[0462] 13 C NMR (CDCl3, 126MHz) δ (ppm) = 176.2, 77.1, 52.2, 40.1, 38.0, 37.8, 32.5, 31.9, 26.1, 22.2, 21.6, 16.2.

[0463] HRMS (GC-EI) m / z C 12 H 20 O2 + [M] + Calculated value: 196.1458; measured value: 196.1458.

[0464] GC DB-Waxetr 0.25 mm / 0.25 mm, 30 m, temperature: 220 °C (injector) / 60 °C to 135 °C at 2 °C / min, then 6 °C / min to 220 °C, then 12 °C / min to 260 °C, then 5 min at 260 °C, 350 °C (detector), gas: 0.60 bar H2, sample volume: 0.2 μL, t R =31.63min (99%; GC-MS: m / z[M] + =196).

[0465] The aroma effect of the thus obtained (E)-methyl 2-(2,2,6-trimethylcyclohexylidene)acetate (3) was evaluated and designated as sample S11.

[0466] Example 8: Preparation of allyl 2-(2,2,6-trimethylcyclohex-2-en-1-yl)acetate (α / β-5)

[0467]

[0468] A 20mL headspace Biotage microwave reactor vial was charged with a PTFE-coated magnetic stirring bar and anhydrous K2CO3 (256mg, 1.85mmol, 1.25 equivalents). The vial was sealed with a rubber septum, evacuated, flame dried, and backfilled with argon after cooling to room temperature. Carboxylic acid (isomer mixture α:β=57:43; 270mg, 1.48mmol, 1.0 equivalents) and anhydrous acetone (7.5mL) were added successively. Allyl bromide (224mg, 1.85mmol, 1.25 equivalents) was transferred to the stirred colorless suspension. The rubber septum was replaced and sealed with a crimping cap containing a PTFE-silicone septum. The reaction vessel was immersed in a preheated oil bath at 70°C, and the resulting colorless suspension was vigorously stirred (1400rpm) at this temperature for 90min. After cooling to room temperature, the vial was opened, the colorless reaction mixture was diluted with MTBE (5 mL), and filtered onto diatomaceous earth through absorbent cotton (the reaction vial was rinsed with 4 × 5 mL MTBE). The suspension was concentrated under reduced pressure, and directly purified by flash column chromatography on silica gel (50 g, d × l = 3 × 15 cm) using hexane / MTBE (19: 1 v / v) as eluent to obtain the desired product as a colorless oil (288 mg, 1.30 mmol, 88% yield; 99% GC purity; α-5: β-5 = 55: 45).

[0469] Characterization data of individual isomers:

[0470] α-5:

[0471] 1H NMR (501MHz, CDCl3) δ (ppm) = 5.93 (ddt, J = 17.3, 10.4, 5.8Hz, 1H), 5.36–5.33 (m, 1 H),5.33(dq,J=17.0,1.5Hz,1H),5.24(dq,J=10.3,1.3Hz,1H),4.58(dt,J=6.0,1. 3Hz,2H),2.38(dd,J=17.4,8.2Hz,1H),2.27–2.19(m,2H),2.01–1.92(m,2H),1.66 (q,J=1.9Hz,3H),1.42–1.32(m,1H),1.23–1.14(m,1H),0.92(s,3H),0.84(s,3H).

[0472] 13 C NMR (126MHz, CDCl3) δ (ppm) = 174.2, 135.3, 132.4, 121.6, 118.4, 65.3, 45.7, 35.9, 32.4, 31.5, 27.0, 26.4, 23.0, 22.9.

[0473] Beta-5:

[0474] 1 H NMR (501MHz, CDCl3) δ (ppm) = 5.92 (ddt, J = 17.2, 10.4, 5.7Hz, 1H), 5.32 (dq, J = 17.2, 1.6Hz, 1H), 5.22 (dq, J = 10.4, 1.4Hz, 1H), 4 .57(dt,J=5.7,1.4Hz,2H),3.08(s,2H),1.99(t,J=6.4Hz,2H),1.63–1.56(m,2H),1.59(s,3H),1.48–1.44(m,2H),0.96(s,6H).

[0475] 13 C NMR (126MHz, CDCl3): δ (ppm) 172.6, 132.6, 131.7, 130.5, 118.1, 65.2, 39.5, 34.9, 33.9, 32.9, 28.1, 20.5, 19.5.

[0476] GC DB-1 0.25 mm / 0.25 mm, 30 m, temperature: 220 °C (injector) / 50 °C to 140 °C at 2 °C / min, then to 350 °C at 12 °C / min, 350 °C (detector), gas: 0.60 bar H2, split ratio 120:1, sample volume: 0.2 μL; t R(α-isomer) = 41.0 min (54%; GC-MS: m / z [M] + =222), t R (β-isomer) = 41.3 min (44%; GC-MS: m / z [M] + =222); 99% GC purity.

[0477] HRMS (GC-EI) m / z C 14 H 22 O2 + [M] + Calculated value: 222.1614; measured value: 222.1614.

[0478] The aroma effect of allyl 2-(2,2,6-trimethylcyclohex-2-en-1-yl)acetate (α / β-5) thus obtained was evaluated and designated as sample S12.

[0479] Example 9: Preparation of (±)-1-hydroxy-2,2,6-trimethylcyclohexaneacetic acid methyl ester (4)

[0480]

[0481] Under argon, freshly distilled diisopropylamine (1.59 g, 15.7 mmol, 1.7 equivalents) was transferred to a flame-dried two-necked round-bottom flask equipped with a rubber septum and an argon outlet. Anhydrous THF (15 mL) was added and the flask was immersed in a dry ice / acetone cooling bath at -78 ° C. After 10 min, n-butyl lithium (2.5 M solution in n-hexane, 4.30 g, 15.5 mmol, 1.7 equivalents) was added dropwise, and the resulting yellow solution was stirred at this temperature for 15 min. Subsequently, anhydrous methyl acetate (1.02 g, 13.8 mmol, 1.5 equivalents) was added dropwise and stirring continued for an additional 30 min at -78 ° C. Then, a solution of commercially available 2,2,6-trimethylcyclohexan-1-one (1.29 g, 9.21 mmol, 1.0 equivalents) in THF (10 mL) was added, and the reaction mixture was stirred for another 2 h at -78 ° C. After this time, add saturated aqueous ammonium chloride solution (20mL), then add water (20mL) and MTBE (20mL). Separate organic phase, and extract with aqueous phase MTBE (3×20mL). Wash the combined organic layer with brine (50mL), through Na2SO4 drying, filter and concentrate under reduced pressure, to give a crude product as a light yellow oil, which is a mixture of diastereomers. Purify by flash column chromatography on silica gel (gradient elution with hexane / MTBE 39:1 to 19:1v / v), except mixed fractions (863mg, 4.03mmol, 44% yield), obtain the diastereomer-pure equatorial isomer 4 (912mg, 4.26mmol, 46% yield) as colorless oil, wherein 4:epi-4=2.7:1. This corresponds to a yield of 78% for 4 and a yield of 12% for epi-4, and an overall yield of 90%. The fragrance effect of the thus obtained 4 was evaluated and designated as sample S13.

[0482] Characterization data of major diastereomer 4:

[0483]

[0484] 1 H NMR (CD2Cl2, 600MHz) δ (ppm) = 4.17 (s, 1H), 3.67 (s, 3H), 2.54 (d, J = 15.7Hz, 1H), 2.37 (d, J = 15.7Hz, 1H), 1.79–1.70 (m,2H),1.54–1.38(m,3H),1.32–1.27(m,1H),1.06–1.00(m,1H),0.93(s,3H),0.90(s,3H),0.81(d,J=6.7Hz,3H).

[0485] 13C NMR (CD2Cl2, 151MHz) δ (ppm) = 175.9, 76.2, 52.2, 39.3, 37.4, 37.2, 36.9, 31.1, 25.8, 22.9, 22.1, 16.6.

[0486] HRMS (GC-EI) m / z C 12 H 22 O3 + [M] + Calculated value: 214.1563; measured value: 214.1559.

[0487] The minor diastereomer epi-4 1 H and 13 C NMR data:

[0488]

[0489] 1 H NMR (CD2Cl2, 501MHz) δ (ppm) = 4.63 (s, 1H), 3.68 (s, 3H), 2.56 (d, J = 16.0Hz, 1H), 2.48 (d, J = 16.0Hz, 1H), 1.95 (dqd, J = 13.5, 6.8, 3.8Hz, 1H), 1.60–1 .56(m,1H),1.55–1.48(m,1H),1.46–1.42(m,1H),1.37–1.32(m,2H),1.07 (qd,J=13.2,5.1Hz,1H),1.01(s,3H),0.86(d,J=6.8Hz,3H),0.86(s,3H).

[0490] 13 C NMR (CD2Cl2, 151MHz) δ (ppm) = 176.2, 77.1, 52.2, 40.1, 38.0, 37.8, 32.5, 31.9, 26.1, 22.2, 21.6, 16.2.

[0491] 3. Olfactory effect

[0492] In order to test the quality and strength of the compounds and mixtures of the present invention, an aroma bar test was performed.

[0493] For this purpose, absorbent paper strips were soaked in solutions containing 1 to 10 wt.% of the compound to be tested in triethyl citrate. After evaporation of the solvent (approximately 30 s), the aroma effect was olfactorily evaluated by a trained perfumer.

[0494] The fragrance effects of the mixtures comprising the compound of formula (Ia) and the compound of formula (Ib) prepared according to the present invention are indicated in the following Table I. The compounds were formulated in perfume compositions according to Table II and Table III and are marked as Compound A.

[0495] Compounds according to the compounds of formula (Ia), (Ib) and (Ic) are:

[0496]

[0497] Table I: Fragrance effects of the mixtures

[0498]

[0499]

[0500] 4. Favorable composition

[0501] The mixtures / compounds as indicated in Table I were formulated into compositions according to Table II and Table III. The mixtures indicated in Table I are labeled "Compound A" in Table II and Table III.

[0502] Table II: Compositions 1A and 1B

[0503]

[0504]

[0505] Table III: Compositions 2A and 2B

[0506]

[0507] The compositions according to Table II and Table III (i.e., 1A, 1B, 2A, 2B) can be included in various compositions selected from the group consisting of: deodorant pump spray, cleansing conditioner, cleansing gel, foam bath concentrate, hair spray, self-foaming shower gel, sprayable sun care lotion, sprayable sun protection lotion, moisturizing cleansing gel, 2-phase oil foam bath, shampoo, shower gel, hydro-alcohol AP / deodorant pump spray, aerosol, hydro / alcohol AP / deodorant roll-on, "out of bed" type fixed gel, shaving foam, baby shampoo for sensitive skin, body wash for sensitive skin, shine enhancing shampoo for sensitive scalp, deodorant stick, baby wipes, after shave balm, facial gel, facial day care cream, facial cleanser, body lotion, sunscreen SPF50+, sprayable emulsion, hand dishwashing detergent - regular, hand dishwashing detergent - concentrate, sanitary cleaner - concentrate, multi-purpose cleaner, antibacterial fabric softener, detergent composition, powder detergent composition and liquid detergent composition.

[0508] Those skilled in the art may be familiar with various common formulations of the above-mentioned products.

[0509] Compositions 1A, 1B, 2A and 2B can, for example, be formulated in specific formulations as disclosed in IP.com No.: IPCOM000258614D, entitled New Aroma Chemicals, pages 6 to 46, Tables 1 to D13, wherein "fragrance composition 1A" is replaced by the same amount of composition 1A, 1B, 2A or 2B.

Claims

1. At least one compound having formula (I) or a stereoisomer thereof for imparting a fragrance effect to a composition, in, X1 and X3 together form a double bond between the carbon atoms to which they are bonded, provided that X2 and X4 are hydrogen; or X3 and X4 together form a double bond between the carbon atoms to which they are bonded, provided that X1 and X2 are hydrogen; or X2 and X3 together form a double bond between the carbon atoms to which they are bonded, provided that X1 and X4 are hydrogen; or X4 is OH, X1, X2 and X3 are all hydrogen, Wherein R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

2. The use according to claim 1, wherein Compounds having formula (I) include: At least one compound having formula (Ia) or a stereoisomer thereof or a mixture of stereoisomers thereof, or at least one compound of formula (Ib), A compound having formula (Ib), or at least one compound of formula (Ic), or a stereoisomer thereof or a mixture of stereoisomers thereof, or at least one compound having formula (Id) or a stereoisomer thereof or a mixture of stereoisomers thereof, or a mixture thereof; in, R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

3. The use according to any one of claims 1 to 2, wherein R is selected from methyl, ethyl, propyl, butyl, isobutyl, isopropyl, 1-propenyl, or 2-propenyl.

4. The use according to any one of claims 1 to 3, wherein R is selected from methyl, ethyl or 1-propenyl.

5. Use of the mixture according to claims 2 to 4, wherein The weight ratio of the at least one compound having formula (Ia) to the at least one compound having formula (Ib) is in the range of 0.1:99.9 to 99.9:0.

1.

6. Use of a mixture according to any one of claims 2 to 5, wherein The weight ratio of the at least one compound having formula (Ia) to the at least one compound having formula (Ib) is in the range of 40:60 to 60:

40.

7. Use of a mixture according to any one of claims 2 to 6, wherein The mixture has a ratio ranging from 90:10 to 99.9:0.1, wherein the ratio represents the combined amount of the compound having formula (Ia) and the compound having formula (Ib) to the compound having formula (Ic).

8. A method for imparting a fragrance effect to a composition, the method comprising at least the step of adding a compound of formula (I) according to any one of claims 1 to 7 to the composition.

9. The use or method according to any one of claims 1 to 8, wherein The aromatic effect is selected from the group consisting of woody notes, fruity notes, herbal notes, green leaf notes, root notes, citrus notes, petitgrain notes, floral notes, damascena notes, tobacco notes, ashtray notes, gourmet notes, sweet notes, vanilla root notes, ionone notes, ambergris notes, fresh notes, natural notes, fir needle notes, camphor notes, or any combination of two or more of these notes.

10. The use or method according to any one of claims 1 to 9, wherein The at least one compound having formula (I) is used in a total amount ranging from ≧0.001 wt. % to ≦70.0 wt. %, based on the total weight of the composition.

11. A composition comprising: i) at least one compound of formula (I) according to any one of claims 1 to 7, and ii) at least one aroma chemical (X) other than a compound of formula (I), or iii) at least one non-aroma chemical carrier, or iv) Both (ii) and (iii).

12. The composition according to claim 11, wherein The at least one compound according to any one of claims 1 to 7 is present in the range of ≥ 0.01 wt.% to ≤ 70.0 wt.%, based on the total weight of the composition.

13. The composition according to claim 11, wherein The at least one non-fragrance chemical carrier (ii) is selected from a surfactant, an oil component, an antioxidant, a deodorant active agent, or a solvent.

14. The composition according to any one of claims 11 to 13, wherein The composition is selected from a perfume composition, a body care composition, a hygiene product, a cleaning composition, a textile detergent composition, a composition for a fragrance dispenser, a food, a food supplement, a pharmaceutical composition, or a crop protection composition.

15. A mixture comprising at least one compound of formula (Ib), or a stereoisomer thereof or a mixture of stereoisomers thereof, and At least one compound having formula (IV) or a stereoisomer thereof or a mixture of stereoisomers thereof, wherein R is selected from C1-C5 straight chain or branched chain alkyl and C3-C5 straight chain or branched chain alkenyl.

16. A method for preparing a mixture of at least one compound of formula (I) according to any one of claims 1 to 7, the method comprising at least the following steps: a) cyclizing a compound of formula (III) using a catalytic amount of an acid, wherein R is selected from C1-C5 straight chain or branched alkyl and C3-C5 straight chain or branched alkenyl, to produce the at least one compound of formula (I), b) optionally purifying the at least one compound of formula (I).

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