Fragrance and flavour materials

Abstract

Provided herein are the synthesis and applications of compounds having unique and desirable flavor and / or fragrance profiles. The compounds herein can be used alone or incorporated into a flavor or fragrance composition as a flavor or fragrance ingredient. The present application also relates to consumer products comprising such derivatives and / or flavor or fragrance compositions.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 62 / 680,294, filed on June 4, 2018, which is hereby incorporated by reference in its entirety. Technical Field

[0003] The present application relates to compounds for use as flavors or fragrances in flavor or fragrance compositions. Background of the Invention

[0005] There is a continuing interest in creating novel flavor and fragrance compounds to provide pleasing organoleptic properties in novel flavor and fragrance compositions. For a wide variety of consumer products, the decision to purchase a product can be based on whether the product's smell or taste is pleasing to the consumer. Thus, there remains a need and demand for unique flavor and fragrance compositions having pleasing and consumer-preferred smell and taste characteristics for use in consumer products. SUMMARY OF THE INVENTION

[0007] It is well known in the flavor and fragrance industry that small changes in the chemical structure of a compound can affect its sensory properties in surprising and unpredictable ways. The present disclosure relates to the synthesis and use of compounds with unique and desirable aroma and / or flavor characteristics. The compounds of the present disclosure can be used alone or incorporated into flavor or fragrance compositions.

[0008] In certain embodiments, the present disclosure provides flavor or fragrance compounds represented by Formula Ia:

[0009]

[0010] wherein R1 can be H, alkyl or C(O)R7, R2 can be H, alkyl, alkenyl, alkynyl, straight or branched aryl, R3 can be H, alkyl, alkenyl, alkynyl, straight or branched aryl, R4 can be H, alkyl, alkenyl, alkynyl, straight or branched aryl, R5 can be H or alkyl, R6 can be cyclohexyl, cyclohexenyl or bicyclo[2.2.1]hept-5-enyl, R7 can be H, alkyl, alkenyl, alkynyl, straight or branched aryl, and wherein the compound of Formula Ia can exist as a racemate, a pure stereoisomer, enantiomer or diastereomer thereof, or in the form of a mixture of stereoisomers, enantiomers or diastereomers in any mixing ratio.

[0011] In a specific embodiment, the present disclosure provides a flavor or fragrance compound represented by Formula Ia, wherein R1 can be H, alkyl or C(O)R7, R2 can be alkyl, alkenyl, alkynyl, linear or branched aryl, R3 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl, R4 can be H, C2-C6 alkyl, alkenyl, alkynyl, linear or branched aryl, R5 can be H or alkyl, R6 can be bicyclo[2.2.1]hept-5-enyl and R7 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl.

[0012] In certain other embodiments, the present disclosure provides a flavor or fragrance compound represented by Formula Ia, wherein R1 can be H, alkyl or C(O)R7, R2 can be alkyl, alkenyl, alkynyl, linear or branched aryl, R3 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl, R4 can be alkyl, alkenyl, alkynyl, linear or branched aryl, R5 can be H or alkyl, R6 is cyclohexenyl, and R7 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl.

[0013] In certain other embodiments, the present disclosure provides a flavor or fragrance compound represented by Formula Ia, wherein R1 can be H, alkyl or C(O)R7, R2 can be H, C2-C6 alkyl, alkenyl, alkynyl, linear or branched aryl, R3 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl, R4 can be H, C2-C6 alkyl, alkenyl, alkynyl, linear or branched aryl, R5 can be H or alkyl, R6 can be cyclohexenyl, R7 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl.

[0014] In certain other embodiments, the present disclosure provides a flavor or fragrance compound represented by Formula Ia, wherein R1 can be alkyl or C(O)R7, R2 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl, R3 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl, R4 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl, R5 can be H or alkyl, R6 can be cyclohexenyl, and R7 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl.

[0015] In certain other embodiments, the present disclosure provides a flavor or fragrance compound represented by Formula Ia, wherein R1 can be H, alkyl or C(O)R7, R2 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl, R3 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl, R4 can be C3-C6 alkyl, alkenyl, alkynyl, linear or branched aryl, R5 can be H or alkyl, R6 can be cyclohexyl, and R7 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl.

[0016] In certain other embodiments, the present disclosure provides a flavor or fragrance compound represented by Formula Ia, wherein R1 can be an alkyl group, R2 can be H, an alkyl group, an alkenyl group, an alkynyl group, a linear or branched aryl group, R3 can be H, an alkyl group, an alkenyl group, an alkynyl group, a linear or branched aryl group, R4 can be H, an alkyl group, an alkenyl group, an alkynyl group, a linear or branched aryl group, R5 can be H or an alkyl group, and R6 can be a cyclohexyl group.

[0017] In certain other embodiments, the present disclosure provides a flavor or fragrance compound represented by Formula Ia, wherein R1 can be C(O)R7, R2 can be H, C2-C6 alkyl, alkenyl, alkynyl, linear or branched aryl, R3 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl, R4 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl, R5 can be H or alkyl, R6 can be cyclohexyl, and R7 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl

[0018] In certain other embodiments, the presently disclosed subject matter provides compounds of Formula Ib:

[0019]

[0020] wherein n can be 1 or 2, R1 can be H, alkyl or C(O)R7, R2 can be alkyl, alkenyl, alkynyl, straight or branched aryl, R3 can be alkyl, alkenyl, alkynyl, straight or branched aryl, R4 can be H, alkyl, alkenyl, alkynyl, straight or branched aryl, R5 can be H or alkyl, R6 can be cyclohexyl, cyclohexenyl or bicyclo[2.2.1]hept-5-enyl, R7 can be H, alkyl, alkenyl, alkynyl, straight or branched aryl, and wherein the compound of formula Ib can be in the form of a racemate, a pure stereoisomer, enantiomer or diastereomer thereof, or in the form of a mixture of stereoisomers, enantiomers or diastereomers in any mixing ratio.

[0021] In certain embodiments, the presently disclosed subject matter provides compounds of Formula IIa:

[0022]

[0023] wherein X may be O, NOH, NOCH3 or NOCH2(CO)CH3, R2 may be H, alkyl, alkenyl, alkynyl, straight-chain or branched aryl, R3 may be H, alkyl, alkenyl, alkynyl, straight-chain or branched aryl, R5 may be H or alkyl, R6 may be cyclohexyl, cyclohexenyl or bicyclo[2.2.1]hept-5-enyl, and wherein the compound of formula IIa may be in the form of a racemate, a pure stereoisomer, enantiomer or diastereomer thereof, or in the form of a mixture of stereoisomers, enantiomers or diastereomers in any mixing ratio.

[0024] In certain other embodiments, the present disclosure provides a flavor or fragrance compound represented by formula IIa, wherein X can be NOH, NOCH3 or NOCH2(CO)CH3, n can be 1 or 2, R2 can be H, R3 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl, R5 can be H, alkyl, and R6 can be cyclohexyl, cyclohexenyl or bicyclo[2.2.1]hept-5-enyl.

[0025] In certain other embodiments, the present disclosure provides a flavor or fragrance compound represented by formula IIa, wherein X can be NOCH3 or NOCH2(CO)CH3, n can be 1 or 2, R2 can be alkyl, alkenyl, alkynyl, linear or branched aryl, R3 can be H, alkyl, alkenyl, alkynyl, linear or branched aryl, R5 can be H, alkyl, and R6 can be cyclohexyl, cyclohexenyl or bicyclo[2.2.1]hept-5-enyl.

[0026] In certain other embodiments, the presently disclosed subject matter provides compounds of Formula lib:

[0027]

[0028] wherein X can be O, NOH, NOCH3 or NOCH2(CO)CH3, n can be 1 or 2, R2 can be alkyl, alkenyl, alkynyl, straight-chain or branched aryl, R3 can be alkyl, alkenyl, alkynyl, straight-chain or branched aryl, R5 can be H or alkyl, R6 can be cyclohexyl, cyclohexenyl or bicyclo[2.2.1]hept-5-enyl, and wherein the compound of formula IIb is in the form of its racemate, its pure stereoisomer, enantiomer or diastereomer, or in the form of a mixture of stereoisomers, enantiomers or diastereomers in any mixing ratio.

[0029] In certain other embodiments, the present disclosure provides a flavor or fragrance compound represented by formula IIb, wherein X can be O, NOH, NOCH3 or NOCH2(CO)CH3, n can be 1 or 2, R2 can be an alkyl, alkenyl, alkynyl, a linear or branched aryl group, R3 can be an alkyl, alkenyl, alkynyl, a linear or branched aryl group, R5 can be an alkyl group, and R6 can be a cyclohexyl, cyclohexenyl or bicyclo[2.2.1]hept-5-enyl group.

[0030] In certain embodiments, the presently disclosed subject matter provides compounds of Formula IIIa:

[0031]

[0032] wherein R3 can be H, alkyl, alkenyl, alkynyl, straight-chain or branched aryl, R5 can be H, alkyl, and R6 can be cyclohexyl, cyclohexenyl or bicyclo[2.2.1]hept-5-enyl; and wherein the compound of formula IIIa is in the form of a racemate, a pure stereoisomer, enantiomer or diastereomer, or a mixture of stereoisomers, enantiomers or diastereomers in any mixing ratio.

[0033] The presently disclosed subject matter also provides flavor or fragrance compositions comprising one or more compounds of Formula Ia, Formula Ib, Formula IIa, Formula IIb, or Formula IIIa.

[0034] In certain embodiments, the present disclosure provides fragrance compositions wherein the concentration of the compound of Formula Ia, Formula Ib, Formula IIa, Formula IIb, or Formula IIIa can be from about 0.01% to about 20% by weight of the fragrance composition.

[0035] In certain embodiments, the present disclosure provides a fragrance composition comprising one or more compounds of Formula Ia, Formula Ib, Formula IIa, Formula IIb or Formula IIIa, and further comprising one or more compounds selected from the group consisting of one or more aldehyde compounds, one or more meaty compounds, one or more balsamic compounds, one or more citrus compounds, one or more floral compounds, one or more fruity compounds, one or more gourmand compounds, one or more green compounds, one or more herbal compounds, one or more marine compounds, one or more mossy compounds, one or more musk compounds, one or more rosin compounds, one or more powdery compounds, one or more spicy compounds and / or one or more woody and / or ambery compounds, and combinations thereof.

[0036] In certain other embodiments, the present disclosure provides a fragrance composition wherein the concentration of the compound of Formula Ia, Formula Ib, Formula IIa, Formula IIb or Formula IIIa can be from about 0.001% to about 20% by weight of the fragrance composition. In a specific embodiment, the fragrance composition can further comprise a loaded fragrance.

[0037] Another aspect of the present disclosure provides a consumer product that may include one or more compounds of Formula Ia, Formula Ib, Formula IIa, Formula IIb, or Formula IIIa. In certain other embodiments, the present disclosure provides a consumer product that may include a fragrance or flavor composition comprising one or more compounds of Formula Ia, Formula Ib, Formula IIa, Formula IIb, or Formula IIIa. Detailed Description of the Invention

[0039] As noted above, there remains a need in the art for unique flavor and fragrance compositions. The presently disclosed subject matter addresses these needs through the compounds disclosed herein and / or novel flavor and fragrance compositions comprising one or more of the disclosed compounds.

[0040] For purposes of clarity, and not limitation, the detailed description is divided into the following subsections:

[0041] 1. Definition;

[0042] 2. Flavor and flavor compounds;

[0043] 3. Flavor composition;

[0044] 4. Use of fragrance compositions in consumer products; and

[0045] 5. Fragrance composition.

[0046] 1. definition

[0047] The terms used in this specification generally have their ordinary meanings in the art within the context of this specification and in the specific context in which each term is used. Certain terms are discussed below or elsewhere in the specification to provide additional guidance to those skilled in the art to describe the compounds, compositions, and methods of the present disclosure and how to prepare and use them.

[0048] As used herein, when used in conjunction with the term "comprising" in the claims and / or the specification, the use of the words "a" and "an" can mean "one," but is also consistent with the meaning of "one or more," "at least one," and "one or more than one." Furthermore, the terms "having," "including," "containing," and "comprising" are interchangeable, and those skilled in the art will recognize that these terms are open-ended terms.

[0049] The term "about" or "approximately" means within an acceptable error range for a particular value, as determined by one of ordinary skill in the art, which error range will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, according to practice in the art, "about" can mean within 3 or more standard deviations. Alternatively, "about" can mean a range of at most 20%, preferably at most 10%, more preferably at most 5%, and more preferably at most 1% of a given value. Alternatively, particularly with respect to biological systems or processes, the term can mean within an order of magnitude of a value, preferably within 5 times, more preferably within 2 times, of the value.

[0050] As used herein, the term "enantiomers" refers to a pair of stereoisomers that are non-superimposable mirror images of each other. A 1:1 mixture of a pair of enantiomers is a "racemic" mixture or racemate. Where appropriate, the term is used to refer to a racemic mixture.

[0051] As used herein, the term "enantiomerically pure" refers to a sample that consists of a single enantiomer within the limits of detection.

[0052] As used herein, the term "diastereomer" refers to stereoisomers that have at least two asymmetric atoms but are not mirror images of each other. Absolute stereochemistry is specified according to the Cahn-Ingold-Prelog R--S system. When a compound is a pure enantiomer, the stereochemistry of each chiral carbon can be specified by R or S. Resolved compounds whose absolute configuration is unknown can be specified as (+) or (-) based on the direction (right-hand or left-hand) in which they rotate plane polarized light at the wavelength of the sodium D line. The compounds of the presently disclosed subject matter contain one or more asymmetric centers and can therefore produce enantiomers, diastereomers and other stereoisomeric forms that can be defined as (R)- or (S)- based on absolute stereochemistry. The presently disclosed subject matter is intended to include all such possible isomers, including racemic mixtures, optically pure forms and intermediate mixtures. Optically active (R)- and (S)-isomers can be prepared using chiral synthons or chiral reagents or resolved using conventional techniques. If the compound contains a double bond, the substituents can be in E or Z configuration. If the compound contains a disubstituted cycloalkyl, the cycloalkyl substituent may have a cis or trans configuration. All tautomeric forms are also intended to be included.

[0053] As used herein, the term "isomer" refers to different compounds having the same molecular formula but different arrangements and configurations of atoms. Similarly, as used herein, the term "stereoisomer" refers to any of the various stereoisomeric configurations that can exist for a given compound of the presently disclosed subject matter, and includes geometric isomers. It will be understood that substituents can be attached to the chiral center of a carbon atom. Therefore, the subject matter of the present disclosure includes enantiomers, diastereomers, or racemates of a compound. Additionally, as used herein, the term "constitutional isomers" refers to different compounds having the same number and type of atoms but with different atomic connections.

[0054] As used herein, the term "fragrance composition" refers to a mixture comprising one or more fragrance compounds in any form thereof and one or more solvents or co-ingredients. As is known in the art, a fragrance composition comprises one or more fragrance compounds to impart an olfactory note to a consumer product formulation (e.g., a household cleaner, perfume, or other consumer product) to which it is added. In one embodiment, a fragrance composition comprises two or more fragrance compounds which, together with the solvent to which they are added, impart a desired olfactory note (e.g., a hedonistic "tropical" note) to a person in close proximity to the fragrance composition. Generally speaking, co-ingredients belong to the following chemical classes: alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenes, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils of natural or synthetic origin, and are well known to perfumers of ordinary skill in the art. Many of these ingredients are listed in references, such as S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or any latest edition thereof, which is incorporated herein by reference in its entirety.

[0055] As used herein, the term "accord" refers to a mixture of two or more different fragrance compounds that produce a particular smell, odor, or scent. One or more "accords" can be used as part of a fragrance composition.

[0056] As used herein, the term "flavor composition" refers to a composition comprising one or more compounds (e.g., co-ingredients) that provide a desired flavor when combined with a solvent suitable for oral administration and oral consumption. Examples of flavoring co-ingredients typically included in flavor compositions are listed in S. Arctander's Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or any latest edition thereof, each of which is incorporated herein by reference in its entirety. Those skilled in the art of flavors can select them based on their general knowledge and according to the properties of the product to be scented and the desired flavor.

[0057] As used herein, the term "organoleptically effective amount" refers to the amount of a compound in a flavor composition, wherein the individual components will contribute to its characteristic flavor profile.

[0058] As used herein, the term "sensory effect" or "flavor profile" of a flavor composition refers to the sum of the effects of all flavor ingredients present.

[0059] As used herein, the term "consumer product" or "final product" refers to a composition that is in a form ready for consumer use for its intended intended consumer application. A solvent suitable for use in a consumer product is a solvent that, when combined with the other ingredients of the final product, does not render the consumer product unsuitable for its intended consumer use.

[0060] 2. Fragrance and fragrance compounds

[0061] The present disclosure relates to the synthesis and use of fragrance and / or flavor compounds having unique and desirable aroma and / or flavor properties.

[0062] In certain embodiments, the presently disclosed subject matter provides compounds represented by Formula I:

[0063]

[0064] More particularly, in certain embodiments, the presently disclosed subject matter provides compounds of Formula Ia:

[0065]

[0066] Wherein R1 can be H, alkyl or C(O)R7;

[0067] Wherein R2 can be H, alkyl, alkenyl, alkynyl, straight chain or branched aryl;

[0068] Wherein R3 can be H, alkyl, alkenyl, alkynyl, straight chain or branched aryl;

[0069] Wherein R4 can be H, alkyl, alkenyl, alkynyl, straight chain or branched aryl;

[0070] Wherein R5 can be H or alkyl;

[0071] wherein R6 can be cyclohexyl, cyclohexenyl or bicyclo[2.2.1]hept-5-enyl; and

[0072] Wherein R7 can be H, alkyl, alkenyl, alkynyl, straight chain or branched aryl.

[0073] In a specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R2=R3=R5=H, R4=methyl, and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=C(O)R7, R2=R7=methyl, R3=R4=R5=H, and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R2=methyl, R3=R4=R5=H, and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R3=R5=H, R2=R4=methyl, and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R3=R5=H, R2=R4=methyl, and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R3=R5=H, R2=methyl, R4=ethyl, and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R3=R5=H, R2=methyl, R4=vinyl, and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R3=R5=H, R2=methyl, R4=isopropyl, and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R3=R5=H, R2=methyl, R4=propyl, and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R2=R4=R5=H, R3=methyl, and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=C(O)R7, R2=R4=R5=H, R3=methyl, R6=cyclohexenyl, and R7=methyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1 = R3 = methyl, R2 = R4 = R5 = H, and R6 = cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1 = R2 = R5 = H, R3 = R4 = methyl, and R6 = cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1 = R2 = R5 = H, R3 = methyl, R4 = ethyl, and R6 = cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1 = R2 = R5 = H, R3 = methyl, R4 = propyl, and R6 = cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1 = R2 = R5 = H, R3 = methyl, R4 = allyl, and R6 = cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1 = R3 = R4 = R5 = H, R2 = methyl, and R6 = bicyclo[2.2.1]hept-5-enyl.In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=C(O)R7, R2=R7=methyl, R3=R4=R5=H, and R6=bicyclo[2.2.1]hept-5-enyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R2=methyl, R3=R4=R5=H, and R6=bicyclo[2.2.1]hept-5-enyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R3=R5=H, R2=R4=methyl, and R6=bicyclo[2.2.1]hept-5-enyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R3=R5=H, R2=Methyl, R4=ethyl, and R6=bicyclo[2.2.1]hept-5-enyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = vinyl, and R6 = bicyclo[2.2.1]hept-5-enyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = isopropyl, and R6 = bicyclo[2.2.1]hept-5-enyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = propyl, and R6 = bicyclo[2.2.1]hept-5-enyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1 = R2 = R4 = R5 = H, R3 = methyl, and R6 = bicyclo[2.2.1]hept-5-enyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=C(O)R7, R2=R4=R5=H, R3=methyl, R6=bicyclo[2.2.1]hept-5-enyl, and R7=methyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R3=R4=R5=H, R2=methyl, and R6=cyclohexyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=C(O)R7, R2=R7=methyl, R3=R4=R5=H, and R6=cyclohexyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R2=methyl, R3=R4=R5=H, and R6=cyclohexyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R3=R5=H, R2=R4=methyl, and R6=cyclohexyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = ethyl, and R6 = cyclohexyl.In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R3=R5=H, R2=methyl, R4=isopropyl, and R6=cyclohexyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R3=R5=H, R2=methyl, R4=propyl, and R6=cyclohexyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=R2=R4=R5=H, R3=methyl, and R6=cyclohexyl. In another specific embodiment, the present disclosure provides compounds of Formula Ia, wherein R1=C(O)R7, R2=R4=R5=H, R3=R7=methyl, and R6=cyclohexyl.

[0074] In certain other embodiments, the presently disclosed subject matter provides compounds of Formula Ib:

[0075]

[0076] Where n can be 1 or 2;

[0077] Wherein R1 can be H, alkyl or C(O)R7;

[0078] Wherein R2 can be an alkyl, alkenyl, alkynyl, straight chain or branched aryl group;

[0079] Wherein R3 can be alkyl, alkenyl, alkynyl, straight chain or branched aryl;

[0080] Wherein R4 can be H, alkyl, alkenyl, alkynyl, straight chain or branched aryl;

[0081] Wherein R5 can be H or alkyl;

[0082] wherein R6 can be cyclohexyl, cyclohexenyl or bicyclo[2.2.1]hept-5-enyl; and

[0083] Wherein R7 can be H, alkyl, alkenyl, alkynyl, straight chain or branched aryl.

[0084] In a specific embodiment, the present disclosure provides compounds of Formula Ib, wherein n=1, R1=R4=R5=H, R2=R3=methyl and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ib, wherein n=1, R1=C(O)R7, R2=R3=R7=methyl, R4=R5=H and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ib, wherein n=1, R1=R2=R3=methyl, R4=R5=H and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ib, wherein n=2, R1=R4=R5=H, R2=R3=methyl, and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ib, wherein n=2, R1=C(O)R7, R2=R3=R7=methyl, R4=R5=H, and R6=cyclohexenyl. In another specific embodiment, the present disclosure provides compounds of Formula Ib, wherein n=2, R1=R2=R3=methyl, R4=R5=H, and R6=cyclohexenyl.

[0085] In certain embodiments, the presently disclosed subject matter provides compounds represented by Formula II:

[0086]

[0087] More particularly, in certain embodiments, the presently disclosed subject matter provides compounds of Formula IIa:

[0088]

[0089] Wherein X can be O, NOH, NOCH3 or NOCH2(CO)CH3;

[0090] Wherein R2 can be H, alkyl, alkenyl, alkynyl, straight chain or branched aryl;

[0091] Wherein R3 can be H, alkyl, alkenyl, alkynyl, straight chain or branched aryl;

[0092] wherein R5 may be H or alkyl; and

[0093] wherein R6 can be cyclohexyl, cyclohexenyl or bicyclo[2.2.1]hept-5-enyl.

[0094] In one specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = NOH, R2 = methyl, R3 = R5 = H, and R6 = cyclohexenyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = NOCH3, R2 = methyl, R3 = R5 = H, and R6 = cyclohexenyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = O, R2 = R5 = H, R3 = methyl, and R6 = cyclohexenyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = NOH, R2 = R5 = H, R3 = methyl, and R6 = cyclohexenyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = NOCH3, R2 = R5 = H, R3 = methyl, and R6 = cyclohexenyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = O, R2 = methyl, R3 = R5 = H, and R6 = bicyclo[2.2.1]hept-5-enyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = NOCH3, R2 = methyl, R3 = R5 = H, and R6 = bicyclo[2.2.1]hept-5-enyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = O, R2 = R5 = H, R3 = methyl, and R6 = bicyclo[2.2.1]hept-5-enyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = O, R2 = methyl, R3 = R5 = H, and R6 = cyclohexyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = NOH, R2 = methyl, R3 = R5 = H, and R6 = cyclohexyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = NOCH3, R2 = methyl, R3 = R5 = H, and R6 = cyclohexyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = O, R2 = R5 = H, R3 = methyl, and R6 = cyclohexyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = NOH, R2 = R5 = H, R3 = methyl, and R6 = bicyclo[2.2.1]hept-5-enyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIa, wherein X = NOH, R2 = R5 = H, R3 = methyl, and R6 = cyclohexyl.

[0095] In certain other embodiments, the presently disclosed subject matter provides compounds of Formula lib:

[0096]

[0097] Wherein X can be O, NOH, NOCH3 or NOCH2(CO)CH3;

[0098] Where n can be 1 or 2;

[0099] Wherein R2 can be an alkyl, alkenyl, alkynyl, straight chain or branched aryl group;

[0100] Wherein R3 can be alkyl, alkenyl, alkynyl, straight chain or branched aryl;

[0101] wherein R5 may be H or alkyl; and

[0102] wherein R6 can be cyclohexyl, cyclohexenyl or bicyclo[2.2.1]hept-5-enyl.

[0103] In one specific embodiment, the presently disclosed subject matter provides a compound of formula IIb, wherein n=1, X=O, R2=R3=methyl, R5=H, and R6=cyclohexenyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIb, wherein n=2, X=O, R2=R3=methyl, R5=H, and R6=cyclohexenyl.

[0104] In certain embodiments, the presently disclosed subject matter provides compounds represented by Formula III:

[0105]

[0106]

[0107] More particularly, in certain embodiments, the presently disclosed subject matter provides compounds of Formula IIIa:

[0108]

[0109] Wherein R3 can be H, alkyl, alkenyl, alkynyl, straight chain or branched aryl;

[0110] wherein R5 may be H or alkyl; and

[0111] wherein R6 can be cyclohexyl, cyclohexenyl or bicyclo[2.2.1]hept-5-enyl.

[0112] In one specific embodiment, the presently disclosed subject matter provides a compound of formula IIIa, wherein R3 = methyl, R5 = H, and R6 = cyclohexenyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIIa, wherein R3 = methyl, R5 = H, and R6 = bicyclo[2.2.1]hept-5-enyl. In another specific embodiment, the presently disclosed subject matter provides a compound of formula IIIa, wherein R3 = methyl, R5 = H, and R6 = cyclohexyl.

[0113] In certain embodiments, compounds include isomers, enantiomers, stereoisomers, and racemic mixtures of the compounds.

[0114] The compounds disclosed herein may be synthetic or natural. Synthetic forms of the compounds include those obtained by chemical synthesis or isolated by chemical processes, whether artificial or nature-identical. Natural forms of the presently disclosed compounds include those obtained from materials of plant or animal origin by physical, enzymatic and / or microbiological processes, such as fermentation.

[0115] 3. Flavor composition

[0116] In certain embodiments, any of the above-described compounds can be provided in a fragrance composition.Certain embodiments of the presently disclosed subject matter provide methods of altering, enhancing, or improving the odor characteristics of a fragrance composition by adding an effective amount of one or more compounds to the composition.

[0117] For perfume applications, the concentration of the compounds of formula I-III is based on the total weight of the composition into which the perfume compound is incorporated. Typical concentrations of the compounds of the present disclosure in perfume compositions can be in the range of about 0.01% to about 20%, or about 0.01% to about 10%, or about 0.01% to about 5%, or about 0.01% to about 3%, or about 0.01% to about 1%, based on the total weight of the perfume composition into which the perfume compound is incorporated. In a specific embodiment, the compounds of the present disclosure can be present in the perfume composition in an amount of about 0.01%, about 0.1%, about 0.5%, about 0.8%, about 1%, about 3% or about 5% by weight, based on the total weight of the perfume composition. In a further embodiment, the compounds of the present disclosure can be present in the perfume composition in an amount of at least about 0.01%, at least about 0.1%, at least about 0.5%, at least about 1% or at least about 5% by weight, based on the total weight of the perfume composition. Those skilled in the art can adopt the compounds of the present disclosure of the desired level to provide the desired fragrance / flavor and intensity.

[0118] The compounds of the presently disclosed subject matter can be combined with one or more fragrance compounds from various fragrance classes including, but not limited to, one or more aldehyde compounds, one or more meaty compounds, one or more balsamic compounds, one or more citrus compounds, one or more floral compounds, one or more fruity compounds, one or more gourmand compounds, one or more green compounds, one or more herbal compounds, one or more marine compounds, one or more mossy compounds, one or more musk compounds, one or more pine compounds, one or more powdery compounds, one or more spicy compounds and / or one or more woody and / or ambery compounds, and combinations thereof, to form a fragrance accord or fragrance composition.

[0119] In certain embodiments, the fragrance composition may include a compound of Formula I-III and one or more fragrance compounds, including one or more citrus aroma compounds, one or more floral aroma compounds, one or more fruity aroma compounds, one or more gourmet aroma compounds, one or more green aroma compounds, one or more herbal aroma compounds, one or more musk compounds, and one or more woody and / or amber aroma compounds. The compound of Formula I-III may be present in an amount of about 0.0001% to about 5%, about 0.001% to about 5%, or about 0.01% to about 1% by weight, based on the total weight of the fragrance composition. The one or more citrus aroma compounds may be present in an amount of about 1% to about 20%, about 1% to about 15%, or about 1% to about 10%, based on the total weight of the fragrance composition. The one or more floral aroma compounds may be present in an amount of about 1% to about 50%, about 5% to about 45%, or about 15% to about 40%, based on the total weight of the fragrance composition. One or more fruity aroma compounds may be present in an amount of about 1% to about 30%, about 5% to about 25%, about 10% to about 20%, or about 15% to about 20% by weight, based on the total weight of the fragrance composition. One or more gourmand aroma compounds may be present in an amount of about 0.01% to about 5%, about 0.2% to about 2%, or about 0.5% to about 1.5% by weight, based on the total weight of the fragrance composition. One or more green aroma compounds may be present in an amount of about 0.01% to about 5%, about 0.2% to about 3%, or about 0.5% to about 2.5% by weight, based on the total weight of the fragrance composition. One or more herbal aroma compounds may be present in an amount of about 0.01% to about 5%, about 0.1% to about 2%, about 0.2% to about 1.5%, or about 0.3% to about 0.5% by weight, based on the total weight of the fragrance composition. One or more musk compounds may be present in an amount of about 1% to about 10%, about 2% to about 8%, or about 4% to about 6% by weight, based on the total weight of the fragrance composition. One or more woody notes and / or compounds may be present in an amount of about 5% to about 25%, about 10% to about 20%, or about 12% to about 18% by weight, based on the total weight of the fragrance composition. In a specific embodiment, the compound of Formula I-III may be 4-(cyclohex-3-ene-1-yl)but-3-ene-2-yl acetate. In certain embodiments, the one or more solvents may include dipropylene glycol (DPG).

[0120] In certain embodiments, a fragrance composition may include a compound of Formula I-III and one or more fragrance compounds, including one or more aldehyde compounds, one or more citrus compounds, one or more floral compounds, one or more fruity compounds, one or more green compounds, one or more herbal compounds, one or more musk compounds, and one or more rosin compounds. The compound of Formula I-III may be present in an amount of about 1% to about 25%, about 5% to about 15%, or about 10% by weight, based on the total weight of the fragrance composition. The one or more aldehyde compounds may be present in an amount of about 1% to about 10%, about 2% to about 5%, or about 3% to about 4%, based on the total weight of the fragrance composition. The one or more citrus compounds may be present in an amount of about 10% to about 50%, about 20% to about 45%, or about 30% to about 40%, based on the total weight of the fragrance composition. The one or more floral compounds may be present in an amount of about 5% to about 35%, about 15% to about 30%, or about 25%, based on the total weight of the fragrance composition. One or more fruity aroma compounds may be present in an amount of about 0.1% to about 2%, about 0.2% to about 1.5%, or about 0.3% to about 0.5% by weight, based on the total weight of the fragrance composition. One or more green aroma compounds may be present in an amount of about 0.1% to about 2%, about 0.3% to about 1.5%, or about 0.5% to about 1% by weight, based on the total weight of the fragrance composition. One or more herbal aroma compounds may be present in an amount of about 1% to about 10%, about 2% to about 8%, or about 3% to about 5% by weight, based on the total weight of the fragrance composition. One or more musk compounds may be present in an amount of about 1% to about 20%, about 3% to about 15%, or about 5% to about 10% by weight, based on the total weight of the fragrance composition. One or more rosin compounds may be present in an amount of about 5% to about 25%, about 10% to about 20%, or about 12% to about 15% by weight, based on the total weight of the fragrance composition. In a specific embodiment, the compound of Formula I-III can be 4-(cyclohex-3-en-1-yl)but-3-en-2-yl acetate. In certain embodiments, the one or more solvents can include dipropylene glycol (DPG).

[0121] In certain embodiments, a fragrance composition may include a compound of Formula I-III and one or more fragrance compounds, including one or more citrus aroma compounds, one or more floral aroma compounds, one or more fruit aroma compounds, one or more gourmand aroma compounds, one or more green aroma compounds, one or more musk aroma compounds, and one or more woody and / or amber aroma compounds. The compound of Formula I-III may be present in an amount of about 1% to about 25%, about 5% to about 15%, or about 10% by weight, based on the total weight of the fragrance composition. The one or more citrus aroma compounds may be present in an amount of about 1% to about 25%, about 5% to about 20%, or about 10% to about 15% by weight, based on the total weight of the fragrance composition. The one or more floral aroma compounds may be present in an amount of about 15% to about 40%, about 20% to about 35%, or about 25% to about 30% by weight, based on the total weight of the fragrance composition. The one or more fruit aroma compounds may be present in an amount of about 25% to about 50%, or about 30% to about 45%, or about 35% to about 40% by weight, based on the total weight of the fragrance composition. One or more gourmet aroma compounds can be present in an amount of about 0.01% to about 1.5% by weight, or about 0.1% to about 1%, or about 0.5%, based on the total weight of the perfume composition. One or more green aroma compounds can be present in an amount of about 0.01% to about 5%, about 0.2% to about 3% or about 0.5% to about 2.5% by weight, based on the total weight of the perfume composition. One or more musk compounds can be present in an amount of about 0.1% to about 10%, about 1% to about 5%, or about 2% to about 4% by weight, based on the total weight of the perfume composition. One or more woody and / or amber aroma compounds can be present in an amount of about 0.01% to about 5%, about 0.05% to about 2% or about 0.1% to about 1%, based on the total weight of the perfume composition. In a specific embodiment, the compound of Formula I-III can be 4-(cyclohex-3-ene-1-yl)but-3-ene-2-yl acetate. In certain embodiments, one or more solvents may include dipropylene glycol (DPG).

[0122] In certain embodiments, the fragrance composition may include a compound of Formula I-III and one or more fragrance compounds, including one or more citrus aroma compounds, one or more floral aroma compounds, one or more fruit aroma compounds, one or more gourmand aroma compounds, one or more musk compounds, and one or more woody and / or amber aroma compounds. Based on the total weight of the fragrance composition, the compound of Formula I-III may be present in an amount from 0.1% to about 10%, from about 1% to about 5%, or about 2% by weight. The one or more citrus aroma compounds may be present in an amount from about 1% to about 25%, from about 5% to about 20%, or from about 10% to about 15% by weight, based on the total weight of the fragrance composition. The one or more floral aroma compounds may be present in an amount from about 10% to about 50%, from about 20% to about 40%, or from about 30% to about 35% by weight, based on the total weight of the fragrance composition. The one or more fruit aroma compounds may be present in an amount from about 0.01% to about 5%, from about 0.1% to about 2%, from about 0.2% to about 1.5%, or from about 0.3% to about 0.5% by weight, based on the total weight of the fragrance composition. One or more gourmet aroma compounds can be present in an amount of about 0.01% to about 5%, about 0.1% to about 2%, about 0.2% to about 1.5% or about 0.3% to about 0.5%, based on the total weight of the perfume composition. One or more musk compounds can be present in an amount of about 0.0001% to about 5%, about 0.001% to about 3% or about 0.01% to about 1% by weight, based on the total weight of the perfume composition. One or more woody and / or amber aroma compounds can be present in an amount of about 0.01% to about 15%, about 0.1% to about 10% or about 1% to about 5% by weight, based on the total weight of the perfume composition. In a specific embodiment, the compound of formula I-III can be 1-(cyclohex-3-ene-1-yl)-2-methylpent-1-ene-3-ol. In certain embodiments, one or more solvents may include dipropylene glycol methyl ether acetate (DPMA).

[0123] Non-limiting examples of suitable aldehyde aroma compounds include acetaldehyde C-8, acetaldehyde C-9, acetaldehyde C-10, adoc aldehyde, C-8 aldehyde, C-9 aldehyde, C-10 aldehyde, C-11 aldehyde, C-12 aldehyde, C-12 aldehyde lauryl aldehyde, C-12 aldehyde MNA, aldehyde supra, heliotrope, trans-2-decenal, trans-4-decenal, cis-4-decenal, 9-decenal, myristic aldehyde, precyclemone B, trans-2-decenal, undecenal, 1-methyl-4-(4-methylpentyl)cyclohex-3-ene-1-carbaldehyde and combinations thereof.

[0124] Non-limiting examples of suitable meaty aroma compounds include 5-cyclohexadecene-1-one 17-Oxacycloheptadeca-6-en-1-one (Amur cork lactone), 2,5,5-trimethyl-1,3,4,4a,6,7-hexahydronaphthalen-2-ol (Ambroxol), 2-methyl-5-(5,5,6-trimethylbicyclo[2.2.1]hept-2-yl)cyclohexanone Civet, p-cresol, cresol methyl ether, indole, skatole and combinations thereof.

[0125] Non-limiting examples of suitable balsamic fragrance compounds include benzyl salicylate, cyclohexyl salicylate, isopropoxyethyl salicylate, phenethyl salicylate, styrax oil, and combinations thereof.

[0126] Non-limiting examples of suitable citrus aroma compounds include delta-3-carene, citral, citronellal, L-citronellol, decanal, DH-L-citronellal, DH-myristyl alcohol, limonene, myristenol, nootkatone, sinensal, bergamot oil, grapefruit oil, lemon oil, lime oil, orange oil, tridecene-2-carbonitrile and / or yuzu core base.

[0127] Non-limiting examples of suitable floral aroma compounds include ethylanisole, α-amylcinnamaldehyde, anisyl acetate, anisaldehyde, benzyl acetate, bubalan, butyl acetate, hexylcinnamaldehyde, 1-citronellal, cyclamen aldehyde, cyclohexyl lactone, delta-damacron, 9-decen-1-ol, dimethylbenzylmethanol, dimethyloctanol (tetrahydrogeraniol), farnesaldehyde, 1-dihydrofarnesaldehyde, ethyl linalool, 1-farnesaldehyde, farnesol, 1-dihydrofarnesol, 3-(3-isopropylphenyl)butyraldehyde 3-(4-ethylphenyl)-2,2-dimethylpropanal (sea breeze aldehyde), 4-methyl-2-(2-methylpropyl)oxan-4-ol Geraniol, gernayl acetate, piperonal, methyl 3-oxo-2-pentylcyclopentane acetate 2-Methyl-3-(3,4-methylenedioxyphenyl)propanal (heliotropinaldehyde), 1-(5,6,7,8-tetrahydronaphthalen-2-yl)ethanone 3-(4-Isobutyl-phenyl)-2-methyl-propionaldehyde Isobutyl salicylate, hexyl cinnamaldehyde, hexyl salicylate, indole, α-ionone, β-ionone, isopropoxyethyl salicylate, methyl 2-((1S*, 2R*)-3-oxo-2-pentylcyclopentyl)acetate cis-Jasmone, 4-(4-hydroxy-4-methylpentyl)cyclohex-3-ene-1-carbaldehyde Laurinal, lilyral, linalool, linalyl acetate, 2,4,6-trimethyl-4-phenyl-1,3-dioxane 2,4-Dimethyl-4,4a,5,9b-tetrahydroindeno[1,2-d][1,3]dioxin (Magnolan), (4-propan-2-ylcyclohexyl)methanol (Melaleuca alcohol), methyl dihydrojasmonate, γ-methylionone, methyl benzoate, 1-(4-isopropyl-cyclohexyl)ethanol (Mugetanol), nerol, 1-(3-methyl-benzofuran-2-yl)-ethanone (Nerolione), neryl acetate, orantha, L., 2-pentylcyclopentanone, 2-cyclohexyl-2-cyclohexylideneacetonitrile Phenylacetyl alcohol, ethyl phenoxyisobutyrate, phenylacetaldehyde, phenylethyl alcohol, isoprenyl salicylate, rose oxide, rose ketone (rosephenone), aromatic rose oxide (rosyrane), terpineol, methyldecenol, 2,2,5-trimethyl-5-pentylcyclopentane-1-one (Nerolidol (yara yara), geranium oil, rose oil, lavender oil, ylang-ylang oil and combinations thereof.

[0128] Non-limiting examples of suitable fruity aroma compounds include C-16 aldehydes, allyl hexanoate, allyl cyclohexyl propionate, allyl heptanoate, amyl acetate, benzaldehyde, L-Citronellyl acetate, L-citronellyl nitrile, 3a,4,5,6,7,7a-hexahydro-4,7-methano-1h-inden-5(or 6)-yl acetate 3a,4,5,6,7,7a-hexahydro-1H-4,7-methaninden-1-yl propionate Damascenone, β-decanoic acid, γ-decanoic acid, diethyl malonate, dimethylbenzyl methanol acetate, dimethylbenzyl methanol butyrate, dimethylphenylethyl carbinol, dimethyl sulfide, γ-dodecalactone, ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl decadienotate, ethyl heptanoate, ethyl 2-methylbutyrate, ethyl acetoacetate, ethyl methyl phenylglycidate, ethyl propionate, 4-methyl-2-(2-methylpropyl)oxan-4-ol tricyclo[5.2.1.02.6]decane-2-carboxylic acid ethyl ester Hexyl acetate, hexyl isobutyrate, isopentyl acetate, 6-(pent-3-en-1-yl)tetrahydro-2H-pyran-2-one (jasmonate), ethyl 2-methylvalerate (matricaria), 2,6-dimethylhept-5-enal (watermelonal), methyl anthranilate, methyl dioxolane, methyl heptyl ketone, γ-nonalactone, 6-nonenol, γ-octanolactone, phenylethyl isobutyrate, isopentenyl acetate, raspberry ketone, methyl 2-((4S)-4-methyl-2-methylenecyclohexyl)propan-2-yl)sulfane (1R,6S)-2,2,6-Trimethylcyclohexanecarboxylic acid ethyl ester Tolylaldehyde, gamma-undecanolactone, 3,5,5-trimethylhexyl acetate (vanoris), (2-tert-butylcyclohexyl) acetate (verdox), nopal acetate and combinations thereof.

[0129] Non-limiting examples of suitable gourmet aroma compounds include angelica lactone-alpha, octanoic acid, coumarin, ethyl fraison, ethyl vanillin, ethyl maltol (e.g., VELTOL PLUS), hazelnut ketone, 4-hydroxy-2,5-dimethyl-3(2H)-furanone Guaiacol, maple furanone, 2-acetylpyrazine, 2,5-dimethylpyrazine, cyclohex-3-en-1-ylmethyl-2-hydroxypropionate, vanillin, and combinations thereof.

[0130] Non-limiting examples of suitable green aroma compounds include allyl isopentyl acetate, cyclogallate, 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one Galbanolene, galbanum, trans-2-hexenal, cis-3-hexenol, hexen-1-ol, cis-3-hexenyl acetate, cis-3-hexenyl butyrate, cis-3-hexenyl formate, cis-3-hexenyl salicylate, chlorophen, 2-methoxy-2-methylheptane, methyloctyne carbonate, neophylline, 2,6-nonadienal, (2R,4S)-2-methyl-4-propyl-1,3-xanthene Octahydro-5-methoxy-4,7-methyl-1H-indene-2-carbaldehyde N-(5-Methylhept-3-ylidene)hydroxylamine Styryl acetate, 2,4-dimethylcyclohex-3-ene-1-carbaldehyde Undecapentaenol, perilla, violet methyl carbonate (eg, VIOLET T), violet leaf extract, and combinations thereof.

[0131] Non-limiting examples of suitable herbal aroma compounds include bamboo ketone, catechol, carvacrol, sage oil, p-cymene, 2,6-dimethylheptan-2-ol, Menthol, methyl salicylate, thymol, natural basil oil, natural eucalyptus oil, eucalyptol, sweet natural cumin oil, natural cedar leaf oil and combinations thereof.

[0132] Non-limiting examples of suitable marine aroma compounds include 8-methyl-1,5-benzodioxepin-3-one ( 1951), 3-(4-ethylphenyl)-2,2-dimethylpropanal (sea breeze aldehyde), 4-tert-butylphenylacetonitrile 4-[(3E)-4,8-Dimethylnona-3,7-dienyl]pyridine Citrus aldehyde, ultrazure and their combinations.

[0133] Non-limiting examples of suitable moss compounds include hinokitiol, isobutylquinolone, isopropylquinolone and / or methyl 2,4-dihydroxy-3,6-dimethylbenzoate and combinations thereof.

[0134] Non-limiting examples of suitable musk compounds include 17-oxahedetide-6-en-1-one (ammonia lactone), 5-cyclohexadecene-1-one (3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan (Ambroxan), 2,2,6-trimethyl-α-propylcyclohexanepropanol (Dextramber), 16-oxacyclohexadecane-1-one 4,6,6,7,8,8-Hexamethyl-1,3,4,6,7,8-hexahydro-cyclopenta[g]-isochromene ((12E)-1-oxacyclohexadecene-12-en-2-one (Firmenich), [2-[1-(3,3-dimethylcyclohexyl)ethoxy]-2-methylpropyl]propionate (1'R)-3-methyl-5-(2,2,3-trimethylcyclopentan-1-yl)-2-pentanone, (5E)-3-methylcyclopentadeca-5-en-1-one 1,4-dioxahedema-5,17-dione (Musk T), 3-methylcyclopentadeca-1-one (L-Musk ketone), 1-(1,1,2,6-tetramethyl-3-propane-2-yl-2,3-dihydroindan-5-yl)ethanone (TRASEOLIDE TM ), 1-(3,5,5,6,8,8-hexamethyl-6,7-dihydronaphthalen-2-yl)ethanone and combinations thereof.

[0135] Non-limiting examples of suitable rosin compounds include 1-borneol, 1-bornyl acetate, camphor, camphor gum powder, dihydroterpineol, beta-pinene, and combinations thereof.

[0136] Non-limiting examples of suitable powdery aroma compounds include heliotropine and / or whiskey lactone (methyl octanolactone).

[0137] Non-limiting examples of suitable spicy aroma compounds include acetyl isoeugenol, delta-arpropene, cinnamaldehyde, cuminaldehyde, eugenol, isoeugenol, perillaldehyde, cardamom oil, clove oil, ginger extract, black pepper extract, and combinations thereof.

[0138] Non-limiting examples of suitable woody and / or ambery compounds include amber core, amber extreme, amberol, 4aR,5R,7aS,9R)-octahydro-2,2,5,8,8,9a-hexamethyl-4H-4a,9-methazulene[5,6-d]-1,3-dioxole ((3aR,5aS,9aS,9bR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan(oxuran), 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol Ethoxymethoxycyclododecane (BoisambreneForte), 1,1,2,3,3-pentamethyl-2,5,6,7-tetrahydroindan-4-one ((2R,5S,7R,8R)-8-Methoxy-2,6,6,8-tetramethyltricyclo[5.3.1.01,5]undecane Cypress oil, cedar oil, (1S,2R,5S,7R,8R)-2,6,6,8-tetramethyltricyclo[5.3.1.01,5]undecan-8-ol (cedarol), 2,2,6-trimethyl-α-propylcyclohexanepropanol (Dextramber), 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-ol (R,E)-2-Methyl-4-(2,2,3-trimethylcyclopent-3-enyl)but-2-en-1-ol Hinokitiol, DH-ionone β, [((1R,2S)-1-methyl-2-[[(1R,3S,5S)-1,2,2-trimethyl-3-bicyclo[3.1.0]hexyl]methyl]cyclopropyl]methanol 5-But-2-yl-2-(2,4-dimethyl-1-cyclohex-3-enyl)-5-methyl-1,3-dioxane (karanal), 2,4-dimethyl-2-(1,1,4,4-tetramethyltetrahydronaphthalen-6-yl)-1,3-dioxolane 1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one 2-Ethyl-4-[(1R)-2,2,3-trimethyl-3-cyclopenten-1-yl]-(2E)-buten-1-ol (4-tert-Butylcyclohexyl)acetate Patchouli oil, polysantalol, rhubofix, sandalwood, and combinations thereof.

[0139] The amount of total fragrance compounds in a fragrance composition can vary depending on the desired olfactory properties of the resulting fragrance composition. In certain embodiments, the amount of total fragrance compounds in a fragrance composition can be from about 0.1 parts per thousand to about 999 parts per thousand, or from about 0.1 parts per thousand to about 990 parts per thousand, or from about 0.1 parts per thousand to about 900 parts per thousand, or from about 0.1 parts per thousand to about 800 parts per thousand, or from about 1 part per thousand to about 500 parts per thousand. In specific embodiments, a fragrance composition can contain about 0.1 parts per thousand, about 1 part per thousand, about 10 parts per thousand, about 100 parts per thousand, about 500 parts per thousand, about 800 parts per thousand, about 900 parts per thousand, or about 999 parts per thousand of additional fragrance compounds, based on the total weight of the fragrance composition. Expressed differently, in certain embodiments, the amount of additional fragrance compounds can be from about 0.01% to about 99.9%, or from about 0.01% to about 99%, or from about 0.01% to about 90%, or from about 0.01% to about 80%, from about 0.1% to about 50% by weight, based on the total weight of the fragrance composition. In particular embodiments, on a weight basis, the fragrance composition can comprise from about 0.01%, about 0.1%, about 1%, about 10%, about 50%, about 80%, about 90%, or about 99% by weight of additional fragrance compounds, based on the total weight of the fragrance composition.

[0140] Such a composition may comprise at least one ingredient selected from the group consisting of a fragrance carrier and a fragrance base.Such a composition may further comprise at least one fragrance adjuvant.

[0141] Fragrance carriers can be liquid or solid and generally do not significantly alter the olfactory properties of the fragrance ingredients. Some non-limiting examples of fragrance carriers include emulsifying systems, encapsulating materials, natural or modified starches, polymers, gums, pectins, gelatinous or porous cellular materials, waxes and solvents, which are commonly used in fragrance applications.

[0142] A fragrance base is any composition comprising at least one fragrance auxiliary ingredient. Typically, these auxiliary ingredients belong to chemical classes such as, but not limited to, alcohols, aldehydes, ketones, esters, ethers, acetals, oximes, acetates, nitriles, terpenes, saturated and unsaturated hydrocarbons, and essential oils of natural or synthetic origin.

[0143] The fragrance composition according to the subject matter of the present disclosure may be in the form of a simple mixture of the various associated ingredients and a solvent, or may also be in the form of a two-phase system, such as an emulsion or microemulsion. Such systems are well known to those skilled in the art.

[0144] Non-limiting examples of such solvents for use in fragrances are known in the art and include, but are not limited to, dipropylene glycol (DPG), diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2-ethoxy)-1-ethanol, ethyl citrate, triethyl citrate (TEC), ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins (e.g., sold under the trademark (ExxonMobil Chemical, Houston, TX) and glycol ethers and glycol ether esters (such as those known under the trademark (Dow Chemical Company, Midland, Michigan). In a particular embodiment, the solvent may include dipropylene glycol (DPG). In an alternative embodiment, the solvent may include dipropylene glycol (DPG) and triethyl citrate (TEC).

[0145] 4. Use of fragrance compositions in consumer products

[0146] In certain embodiments, the compositions of the present disclosure are formulated as part of a consumer product. Such consumer products can be prepared in any suitable form by any method selected by the formulator. Suitable consumer products that can include compounds of the presently disclosed subject matter include, but are not limited to, air care products (e.g., candles, aerosols, air fresheners, room sprays and mists, liquid electric air fresheners, aroma diffusers, gel air fresheners, plug-in air fresheners and oils, wax melts, and the like); baby care products (e.g., consumer products related to disposable absorbent and / or non-absorbent articles, including adult incontinence garments, bibs, diapers, training pants, infant care wipes; and personal care products, including hand soaps, shampoos, lotions, body washes, and clothing); fabric and home care products (e.g., consumer products for fabric conditioning (including softening), laundry detergents, laundry and rinse additives and / or care, bleaching, dryer sheets, fragrance beads, dishwashing, hard surface cleaning and / or treatment, and other cleansing for consumer and or institutional use); personal care products (e.g., lotions, creams, moisturizers, body washes, hand soaps, shampoos, conditioners, soaps, and the like) ; Home care products (e.g., wet or dry toilet paper, facial tissue, disposable handkerchiefs, disposable towels and / or wipes, towels, facial tissue, wet towels, etc.); Feminine care products (e.g., menstrual pads, incontinence pads, interlabial pads, panty liners, vaginal suppositories, sanitary napkins, tampons and tampon applicators and / or wipes, etc.); Sexual health products (e.g., products related to sexual aids or sexual health, including lubricants and condoms, etc.); Pet care products (e.g., pet odor-smelling cat litter, litter boxes, pet deodorants, pet health and nutrition including pet food, treats, other orally deliverable products, grooming aids, products for treating pet hair / coat including washing, styling, and grooming; deodorants and antiperspirants; products for cleaning or treating pet skin including soaps, creams, lotions, and other topically applied products; training aids, toys, and diagnostic technologies); Fine fragrances (including hydroalcoholic solutions of fragrance oils, such as parfum / extrait perfumes de parfum), perfume (eau de parfum), parfum de toilette, eau de toilette, cologne, body spray (body splash), aftershave, body mists, including baby cologne); car care products (e.g., cleaners, air fresheners, wipes, soaps, etc.); cosmetics (e.g., skin creams, makeup removers, night creams, hand creams, lotions, aftershave, body lotions, foundation, lipstick, lip balm, nail polish, nail polish remover, talcum powder, anti-wrinkle and / or anti-aging cosmetics, sunscreen products, massage oils, etc.); beauty care products (e.g., products for treating human hair, including shampooing, styling, conditioning; deodorants and antiperspirants; products for personal cleansing);Products for treating human skin, including creams, lotions and other topically applied products; shaving products, rinse-off products, shampoo conditioners; hair styling agents such as pomades, conditioners, gels, creams and mousses; hair growth agents; hair dyes, etc.); and bath preparations (e.g., powder bath additives, solid foam bath additives, bath oils, foam bath fragrance generators, bath salts, etc.); depilatory products (e.g., depilatory products, including depilatory creams, sugar pastes or gels, waxes); and topical medications (e.g., ointments, creams, etc. for treating and / or preventing diseases and / or alleviating symptoms in humans and / or animals). Depending on the solvents that may be present in certain final products, it may be necessary to protect the compound from premature degradation, for example, by encapsulation or the use of stabilizers or other methods well known to those skilled in the art.

[0147] In certain embodiments of the present disclosure, a fragrance composition can be mixed with a consumer product, wherein the composition is present in an amount from about 0.0001% to about 90% by weight, or from about 0.001% to about 75% by weight, or from about 1% to about 50% by weight, or from about 5% to about 25% by weight, or from about 10% to about 15% by weight, and values ​​therebetween, based on the total weight of the consumer product. In other embodiments, a fragrance composition can be mixed with a consumer product, wherein the composition is present in an amount from about 0.0001% to about 10% by weight, or from about 0.001% to about 5% by weight, or from about 0.001% to about 1% by weight, based on the total weight of the consumer product.

[0148] In other embodiments, the consumer product can be such that it comprises from about 90% to about 100% by weight, or from about 95% to about 100% by weight, or from about 99% to about 100% by weight of the fragrance composition, based on the total weight of the consumer product. In specific embodiments, the consumer product can be such that it comprises from about 90%, about 95%, about 99% or about 100% by weight of the fragrance composition, based on the total weight of the consumer product.

[0149] In certain embodiments, the consumer product may further comprise one or more bases, solvents, and combinations thereof. As used herein, bases include compositions used in consumer products to achieve a specific purpose of the consumer product, such as cleaning, softening, conditioning, and the like.

[0150] In other embodiments, the matrix and / or solvent of the consumer product may include, but is not limited to, essential oils, lactones, aldehydes, alcohols, ketones, nitriles, esters, terpenes, ethers, acetates, acetals, amides, oximes, and other fragrance ingredients or flavors.

[0151] In some embodiments, the compounds disclosed herein can be used in a consumer product matrix simply by directly mixing at least one compound disclosed herein or a fragrance composition comprising at least one compound disclosed herein, or the compounds described herein can be captured in an earlier step using a capture material such as a polymer, capsule, microcapsule and nanocapsule, liposome, film former, absorbent such as carbon or zeolite, cyclic oligosaccharide and mixtures thereof, or can be chemically bonded to a substrate that is suitable for releasing the fragrance molecules upon application of an external stimulus (such as light, enzyme, etc.) and then mixed with the consumer product matrix.

[0152] In certain embodiments, the fragrance compounds of the present invention can be mixed with consumer products, wherein the disclosed fragrance compounds are present in an amount of from about 0.00001 wt % to about 20 wt %, from about 0.0001 wt % to about 10 wt %, from about 0.001 wt % to about 5 wt %, from about 0.01 wt % to about 3 wt %, and from about 0.001 wt % to about 5 wt %, and values ​​therebetween, based on the total weight of the consumer product. In specific embodiments, the fragrance compounds of the present disclosure can be mixed with consumer products, wherein the disclosed fragrance compounds are present in an amount of at least about 0.00001 wt %, at least about 0.001 wt %, at least about 5 wt %, or at least about 10 wt %, based on the total weight of the consumer product.

[0153] 5. Flavor composition

[0154] In certain embodiments, the compounds of the present disclosure may be provided in the form of a fragrance composition.Certain embodiments of the presently disclosed subject matter provide a method of modifying, enhancing, or improving the odor characteristics of a fragrance composition by adding an effective amount of a compound of the present disclosure to the fragrance composition.

[0155] Those skilled in the art can use the compound of the desired level to provide the desired fragrance and intensity. When these compounds are used in concentrated flavors and flavor compositions, higher concentrations can be used. For flavor applications, the concentration of the compound of Formula I-III is based on the gross weight of the composition into which the compound is incorporated. For flavor applications, the typical concentration of the compound of Formula I-III can be from about 0.00001% to about 20% by weight, or from about 0.0001% to about 5% by weight, or from about 0.001% to about 3% by weight, or from about 0.005% to about 1% by weight, based on the gross weight of the composition into which the compound is incorporated. Those skilled in the art can use the compound of the desired level to provide the desired fragrance and intensity. When the compound is used in concentrated flavors and flavor compositions, higher concentrations can be used.

[0156] The compounds of the present disclosure can be used in more complex flavor compositions containing one or more other flavor ingredients or other flavor compositions to modify the overall odor characteristics of the flavor composition through its own sensory properties or by enhancing or supplementing the contribution of other flavor ingredients present in the composition. Such other flavor ingredients or flavor compositions include, for example, natural or synthetic flavors, i.e., fruit flavors (e.g., lemon, lime, orange, grapefruit; cherry, strawberry, raspberry, cranberry; apple, grape, pineapple, banana, tomato); natural or synthetic plant flavors (e.g., tea flavor, coffee flavor, hazelnut, almond, pecan or other nut flavor; vanilla flavor), and flavor compositions with complex aroma characteristics (e.g., cola flavor or imaginary flavors, such as "birthday cake" or "ice cream sundae"). In such more complex flavor compositions, the amount of the compounds of the present disclosure will vary widely depending on the presence of the other ingredients present, their relative amounts, the desired odor characteristics, and the nature of the consumer product in which the flavor composition will be used.

[0157] Fragrance carriers can be liquid or solid and generally do not significantly alter the olfactory or sensory properties of the fragrance ingredients, respectively. Some non-limiting examples of fragrance carriers include emulsifying systems, encapsulating materials, natural or modified starches, polymers, pectins, proteins, polysaccharides, gums, and solvents, which are commonly used in fragrance applications.

[0158] The fragrance compositions according to the disclosed subject matter can be in the form of simple mixtures of various co-ingredients, adjuvants and solvents, or they can be in the form of two-phase systems, such as emulsions or microemulsions. Such systems are well known to those skilled in the art.

[0159] The flavor composition of the presently disclosed subject matter may further comprise one or more carrier materials. As non-limiting examples, carrier materials may include diluents such as ethanol, purified water, glycerol; and solvent carriers such as propylene glycol, triacetin; preservatives such as sulfites, sodium nitrite, propionic acid, sorbic acid, benzoic acid, disodium ethylenediaminetetraacetic acid (EDTA); flavors such as alcohols, esters, aldehydes; ketones, lactones, phenols, flavor enhancers such as monosodium glutamate (MSG), monopotassium glutamate, calcium diglutamate (CDG), disodium guanosine monophosphate, sodium guanylate, inosinic acid and its salts, L-leucine; antioxidants such as ascorbic acid, sodium ascorbate, ascorbic acid fats, Acid esters, tocopherol, α-tocopherol, γ-tocopherol, δ-tocopherol, propyl gallate, octyl gallate, erythorbic acid, sodium erythorbate, dodecyl gallate, tert-butylhydroquinone (TBHQ), butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), citric acid, 4-hexylresorcinol; color retention agents; dyes or lakes; chelating agents, emulsifiers, such as lecithin, monoglycerides, acetylated monoglycerides, lactated monoglycerides, sugar esters, sorbitan esters, polyglycerol esters, calcium stearoyldilactylate; stabilizer acids, bases and / or anti-caking agents, such as calcium silicate, magnesium carbonate, sodium aluminosilicate. Non-limiting examples of solvents commonly used in fragrances are also known in the art and include, but are not limited to, water, medium chain triglycerides (MCT), propylene glycol, triacetin, triethyl citrate, benzyl alcohol, benzyl benzoate, ethanol, vegetable oils, and terpenes.

[0160] The presently disclosed compounds or flavor compositions of the presently disclosed subject matter can be used in consumer products such as food or beverages, oral care products, animal feed and pet food, and pharmaceuticals (including over-the-counter pharmaceuticals). Examples of suitable consumable products include, but are not limited to, carbonated fruit drinks, carbonated cola drinks, wine coolers, cordials, flavored waters, powdered beverages (e.g., sports powders or "hydration" drinks), fruit-based "smoothie" drinks, milk-based beverages, hard candies, soft candies, toffees, chocolate, sugar-free candies, chewing gum, bubble gum, condiments, spices and flavorings, dry cereals, oatmeal, granola, dressings and preserves, soups, alcoholic beverages, energy drinks, juices, teas, coffees, salsa, gel beads, film strips for bad breath, gelatin candies, pectin candies, starch candies, lozenges, chewable tablets, mint gum, mouthwashes, tooth gels, cough drops, lozenges, throat sprays, toothpaste, mouthwash, nicotine gum, decongestants, oral analgesics, indigestion preparations, and antacids.

[0161] The flavor composition according to the disclosed subject matter can be in the form of a simple mixture of flavor ingredients or in an encapsulated form, for example, a flavor composition embedded in a solid matrix, which can contain wall-forming and plasticizing materials, such as mono-, di- or trisaccharides, natural or modified starches, hydrocolloids, cellulose derivatives, polyvinyl acetate, polyvinyl alcohol, proteins or pectins. Examples of particularly useful matrix materials include, for example, sucrose, glucose, lactose, xylose, fructose, maltose, ribose, dextrose, isomaltulose, sorbitol, mannitol, xylitol, lactitol, maltitol, pentitols, arabinose, pentoses, xylose, galactose, maltodextrin, dextrin, chemically modified starches, hydrogenated starch hydrolysates, succinylated or hydrolyzed starches, agar, carrageenan, gum arabic, gum acacia, gum tragacanth, alginates, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, derivatives, gelatin, agar, alginates, and mixtures thereof. Encapsulation is well known to those skilled in the art and can be performed, for example, using techniques such as spray drying, agglomeration or extrusion, or coating encapsulation, including coacervation and complex coacervation.

[0162] In one embodiment, the compound of the present disclosure theme is included / used for chewing and bubble gum and confectionery (for example, hard candy or soft candy or lozenge).Chewing gum composition usually comprises one or more gum bases and other standard components, such as flavors, softeners, sweeteners etc.The flavors used in chewing gum composition are well-known, and include natural flavors, such as citrus oil, peppermint oil, spearmint oil, wintergreen oil, natural menthol, cinnamon, ginger etc.Artificial flavors, such as menthol, carvone, limonene, cinnamaldehyde, linalool, geraniol, ethyl butyrate etc.As known in the art, the composition used in chewing gum composition can include natural and artificial sweeteners and sugar and sugar-free sweeteners.Based on the gross weight of chewing gum composition, sweetener is usually present in the chewing gum composition in an amount of about 20 weight % to 80 weight %, or about 30 weight % to 60 weight %. Sugarless sweeteners include, but are not limited to, sugar alcohols such as sorbitol, polyphenols, xylitol, hydrogenated starch hydrolysates, maltitol, etc. When used, high intensity sweeteners such as sucralose, aspartame, neotame, salts of acesulfame, etc., are typically present at up to about 1.0% by weight.

[0163] In another alternative embodiment, the compounds of the present disclosure are included in oral personal care products (e.g., mouthwash or toothpaste). For example, a mouthwash can be prepared by dissolving a flavor composition (e.g., flavor mixture) (liquid or powder) including the presently disclosed compounds in a solvent (e.g., water) that also includes, for example, a flavor such as menthol and a surfactant; and then mixing the resulting solution with, for example, an aqueous solution of erythritol.

[0164] In one embodiment of the presently disclosed subject matter, the compounds of the present disclosure are added directly or indirectly to a pharmaceutical dosage form (e.g., tablets, capsules, drops, or lozenges) containing a therapeutically active agent (e.g., a drug). For example, one embodiment of the presently disclosed subject matter provides a cough syrup or lozenge containing one or more compounds of the present disclosure and, optionally, menthol or other drugs for treating sore throats, coughs, or other upper respiratory tract diseases.

[0165] The compounds of the present disclosure can also be added to compositions used, for example, to prepare the following products: 1) carbonated or non-carbonated fruit-flavored beverages, carbonated cola beverages, refreshing drinks, fruit wines, cordials, dairy beverages, milkshakes, smoothie drinks, flavored waters, tropical drinks and "original" mixed drinks (e.g., margaritas, pina coladas, etc.); colada or "Rum Runner" liquor concentrate) and beverage powders (such as sports powders or "hydration" drinks); 2) frozen sweets such as ice cream, sorbet and popsicles; hard candy, soft candy, toffee, chocolate and sugar-free candy; 3) desserts such as jelly and pudding; 4) candy such as cakes, cookies, chewing gum and bubble gum; 5) condiments, spices and seasonings, dry cereal, oatmeal and granola bars; 6) alcoholic beverages, energy drinks, juices, tea, coffee, salsa and gel beads; 7) film strips and oral personal care products for bad breath; 8) gelatin candy, pectin candy, starch candy, lozenges, cough drops, lozenges, throat sprays and toothpaste.

[0166] The compounds of the present disclosure can also be added to, for example, 1) Japanese confectionery, such as bean-filled bread, sweet jelly bean paste bars, and sweet jelly mashed rice; 2) jam; candy 3) bread; 4) beverages, such as green tea, oolong tea, black tea, persimmon leaf tea, chamomile tea, salsa bean tea, mulberry leaf tea, houttuynia tea, Pu'er tea, mate tea, rooibos tea, chocolate tea, guava tea, coffee, espresso, hot and cold espresso, and coffee products obtained by mixing espresso and / or coffee with milk, water, or other liquids suitable for oral administration (e.g., latte, milk coffee, mocha coffee) and cocoa powder; 5) soups, such as Japanese, Western, and Chinese soups; 6) seasonings; 7) various instant beverages and foods; 8) various snack foods; 9) other oral compositions. Example

[0167] The present application is further described by the examples given below, wherein the abbreviations have the usual meanings in the art.

[0168] The use of such examples is illustrative only and does not limit the scope and meaning of the disclosed subject matter or any exemplary terms. Likewise, the disclosed subject matter is not limited to any particular preferred embodiment described herein. Indeed, many modifications and variations of the disclosed subject matter will be apparent to those skilled in the art upon reading this specification. Accordingly, the disclosed subject matter is limited only by the scope of the appended claims and the full scope of equivalents to which such claims are entitled.

[0169] The following examples are provided as specific embodiments of the present disclosure, wherein the abbreviations have the usual meanings in the art. Temperatures are expressed in degrees Celsius (°C); NMR spectral data were recorded in CDCl3 using a 400 MHz instrument. 1 H and 13 C, Chemical shifts are expressed in ppm relative to TMS standard.

[0170] Example 1: Synthesis of 4-(cyclohex-3-en-1-yl)but-3-en-2-one

[0171] Example 1 provides the synthesis of a compound of Formula IIa, wherein X = O, R = methyl, R = R = H, and R = cyclohexenyl. This compound is an intermediate in the synthesis of 4-(cyclohex-3-en-1-yl)but-3-en-2-ol and 4-(cyclohex-3-en-1-yl)but-3-en-2-yl acetate, as described in Examples 2 and 3 below.

[0172] Cyclohex-3-ene-1-carbaldehyde (70 g, 1 eq.), acetone (95.2 mL), 1% NaOH (aq.) (154 mL) and water (126 mL) were combined in a round-bottom flask and heated at 70° C. for 4 hours. The mixture was then cooled to room temperature and an additional 100 mL of water was added. The reaction mixture was extracted with ethyl acetate, dried over MgSO , filtered and concentrated to give 97 g of a crude oil. The oil was distilled (0.07° F., 51° C.) to give 69.6 g of 4-(cyclohex-3-ene-1-yl)but-3-ene-2-one (72.9% yield).

[0173] Example 2: Synthesis of 4-(cyclohex-3-en-1-yl)but-3-en-2-ol

[0174] Example 2 provides the synthesis of a compound of formula Ia, wherein R1 = R2 = R3 = R5 = H, R4 = methyl, and R6 = cyclohexenyl.

[0175] Under a blanket of N2, a mixture of 4-(cyclohex-3-en-1-yl)but-3-en-2-one (65 g, 1 eq.) in anhydrous ether (130 mL) was added dropwise to lithium aluminum hydride (2 M in THF, 125.6 mL, 0.58 eq.). The reaction temperature was maintained below 40°C throughout the addition. The reaction mixture was then stirred at room temperature for 18 hours. The reaction was then cooled to 10°C on an ice and NaCl bath and slowly quenched with water. The resulting precipitate was filtered and washed with ether. The filtrate was concentrated to give 60.9 g of crude 4-(cyclohex-3-en-1-yl)but-3-en-2-ol (92.5% yield). Smell: vanilla, fresh-cut mushroom, sweet, caramel.

[0176] Example 3: Synthesis of 4-(cyclohex-3-en-1-yl)but-3-en-2-yl acetate

[0177] Example 3 provides the synthesis of a compound of Formula Ia, wherein R1 = C(O)R7, R2 = R7 = methyl, R3 = R4 = R5 = H, and R6 = cyclohexenyl.

[0178] 4-(Cyclohex-3-en-1-yl)but-3-en-2-ol (60.9 g, 1 eq.) was combined with acetic anhydride (49.2 mL, 1.3 eq.) and toluene (60 mL) and refluxed for 24 hours. The reaction mixture was then cooled to room temperature, quenched with water, extracted with ether, and washed first with a saturated NaHCO solution and then with brine. The organic extract was dried over MgSO, filtered, and concentrated to give 89.1 g of crude product. Fractional distillation gave 71.8 g of 4-(cyclohex-3-en-1-yl)but-3-en-2-yl acetate (92.4% yield). Smell: citrus, orange, marine. GC / MS (EI): m / z (%) 194 (1), 152 (2), 135 (3), 134 (13), 119 (10), 105 (7), 98 (6), 91 (18), 79 (46), 71 (11), 55 (10), 43 (100). 1 H NMR (CDCl3): δ1.28 (d, 3H), 1.77 (m, 2H), 2.03 (m, 4H), 2.19 (s, 3H), 2.23 (m, 1H), 5.30 (t, 1H), 5.44 (m, 2H), 5.67 (m, 2H). 13 CNMR(CDCl3): δ20.4, 21.5, 24.7, 28.4, 31.0, 36.1, 71.2, 125.9, 126.9, 127.6, 137.8, 170.4.

[0179] Example 4: Synthesis of 4-(3-methoxybut-1-en-1-yl)cyclohex-1-ene

[0180] Example 4 provides the synthesis of a compound of Formula Ia, wherein R1 = R2 = methyl, R3 = R4 = R5 = H, and R6 = cyclohexenyl.

[0181] 4-(Cyclohex-3-en-1-yl)but-3-en-2-ol (1 g, 1 eq) was added to a mixture of KHMDS (1 M in THF, 7.2 mL, 1.1 eq) and 20 mL of THF while heating to 70°C. After 2 hours, iodomethane was added and the reaction mixture was stirred at 70°C for 1 hour. The reaction mixture was then cooled to room temperature, quenched with water, extracted with ether, dried over MgSO4, filtered and concentrated under vacuum. The crude product was purified by Kugelrohr distillation to give 0.62 g of 4-(3-methoxybut-1-en-1-yl)cyclohex-1-ene (56.8% yield). Odor: weak. GC / MS(EI): m / z(%)166(4), 151(6), 134(16), 123(14), 119(16), 111(15), 105(1) 6), 97(62), 91(59), 85(100), 79(89), 71(90), 67(43), 59(59), 55(66), 41(90).

[0182] Example 5: Synthesis of 4-(cyclohex-3-en-1-yl)-2-methylbut-3-en-2-ol

[0183] Example 5 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = R4 = methyl, and R6 = cyclohexenyl.

[0184] A solution of 4-(cyclohex-3-en-1-yl)but-3-en-2-one (1 g, 1 eq.) in 2 mL of anhydrous ether was added dropwise to methylmagnesium bromide (3 M / ether, 2 mL, 1.2 eq.) at room temperature under a nitrogen blanket. The reaction mixture was stirred for 12 hours, then cooled in an ice bath and quenched with saturated NH4Cl. The reaction mixture was then filtered and concentrated in vacuo. The concentrated filtrate was then purified by Kugelrohr distillation (0.4°F, 80°C) to yield 0.74 g of 4-(cyclohex-3-en-1-yl)-2-methylbut-3-en-2-ol (67.3% yield). Odor: Fresh, floral, freesia. GC / MS (EI): m / z (%) 166 (1), 151 (14), 133 (7), 122 (4), 107 (3), 97 (21), 85 (22), 71 (76), 59 (24), 43 (100).

[0185] Example 6: Synthesis of 1-(cyclohex-3-en-1-yl)-3-methylpent-1-en-3-ol

[0186] Example 6 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = ethyl, and R6 = cyclohexenyl.

[0187] The same synthetic protocol as detailed in Example 5 was followed, except that methylmagnesium bromide was replaced by ethylmagnesium bromide (3 M in diethyl ether). 1-(Cyclohex-3-en-1-yl)-3-methylpent-1-en-3-ol was isolated in 65.0% yield. Odor: Sharp, peppery, umami, masculine, aromatic, herbal. GC / MS (EI): m / z (%) 180(1), 162(3), 151(31), 133(5), 119(1), 105(4), 93(14), 81(18), 71(100), 55(13), 43(52).

[0188] Example 7: Synthesis of 1-(cyclohex-3-en-1-yl)-3-methylpenta-1,4-dien-3-ol

[0189] Example 7 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = vinyl, and R6 = cyclohexenyl.

[0190] Following the same synthetic protocol as in Example 5, by replacing methylmagnesium bromide with vinylmagnesium bromide (1M / THF), 1-(cyclohex-3-en-1-yl)-3-methylpenta-1,4-dien-3-ol was isolated in 17.8% yield. Odor: milky, sweet, balsamic, vegetal, gourmand, floral, orchid. GC / MS (EI): m / z (%) 178(1), 160(2), 145(2), 131(3), 120(5), 104(12), 91(32), 79(44), 71(21), 55(27), 43(100).

[0191] Example 8: Synthesis of 1-(cyclohex-3-en-1-yl)-3,4-dimethylpent-1-en-3-ol

[0192] Example 8 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = isopropyl, and R6 = cyclohexenyl.

[0193] The same synthetic protocol as detailed in Example 5 was followed, by replacing methylmagnesium bromide with isopropylmagnesium bromide (2M / THF). 1-(Cyclohex-3-en-1-yl)-3,4-dimethylpent-1-en-3-ol was isolated in 19.4% yield. Odor: Strong, shoe leather, slightly mossy. GC / MS (EI): m / z (%) 194(1), 176(2), 161(1), 151(4), 133(6), 121(5), 113(15), 107(5), 97(2), 91(8), 79(20), 71(21), 55(10), 43(100).

[0194] Example 9: Synthesis of 1-(cyclohex-3-en-1-yl)-3-methylhexyl-1-en-3-ol

[0195] Example 9 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = propyl, and R6 = cyclohexenyl.

[0196] Following the same synthetic protocol as detailed in Example 5, propylmagnesium chloride (1M in 2-methyl-THF) was substituted for methylmagnesium bromide. 1-(Cyclohex-3-en-1-yl)-3-methylhex-1-en-3-ol was isolated in 53.5% yield. Odor: Salty, mossy, bitter grapefruit.

[0197] Example 10: Synthesis of 4-(cyclohex-3-en-1-yl)but-3-en-2-one oxime

[0198] Example 10 provides the synthesis of a compound of formula IIa, wherein X = NOH, R2 = methyl, R3 = R5 = H, R6 = cyclohexenyl.

[0199] Under a nitrogen blanket, 4-(cyclohex-3-en-1-yl)but-3-en-2-one (1 g, 1 eq) was added to hydroxylamine-HCl (0.78 g, 1.7 eq), 20 mL of ethanol, and pyridine (1.08 mL, 2 eq). The reaction mixture was heated to 90°C for 18 hours. After the reaction mixture was cooled to room temperature, the ethanol was removed in vacuo. The remaining mixture was quenched with water and extracted with ethyl acetate, washed first with 1N HCl and then with brine. The extract was dried over MgSO4, filtered, and concentrated to a thick yellow oil. The crude product was purified by Kugelrohr distillation (0.35°F, maximum 100°C) to give 0.14 g of 4-(cyclohex-3-en-1-yl)but-3-en-2-one oxime (12.5% ​​yield). Odor: weak.

[0200] Example 11: Synthesis of O-methyloxime of 4-(cyclohex-3-en-1-yl)but-3-en-2-one

[0201] Example 11 provides the synthesis of a compound of formula IIa, wherein X = NOCH3, R2 = methyl, R3 = R5 = H, and R6 = cyclohexenyl.

[0202] The same synthetic protocol as detailed in Example 10 was followed, substituting O-methylhydroxylamine-HCl for hydroxylamine-HCl. The O-methyloxime of 4-(cyclohex-3-en-1-yl)but-3-en-2-one was isolated in 50.0% yield. Odor: liquorice, aldehyde, floral, green. GC / MS (EI): m / z (%) 179(5), 164(3), 148(20), 132(5), 124(61), 118(4), 110(6), 105(7), 100(7), 94(100), 79(65), 70(16), 65(36), 53(79), 42(77).

[0203] Example 12: Synthesis of 3-(cyclohex-3-en-1-yl)-2-methylacrolein

[0204] Example 12 provides the synthesis of a compound represented by Formula IIa, wherein X = O, R2 = R5 = H, R3 = methyl, and R6 = cyclohexenyl.

[0205] Cyclohexyl-3-ene-1-carbaldehyde (20 g, 1 eq.) was added to NaOH (2.17 g, 0.3 eq.) and water (60 mL), and the reaction mixture was heated to 35°C. Propionaldehyde (11.6 g, 1.1 eq.) was added dropwise, and the reaction mixture was heated at 80°C for 16 hours. Afterwards, the reaction mixture was cooled to room temperature, and 100 mL of water was added. The reaction mixture was extracted with ether, washed with 1N HCl and then brine, dried over MgSO₄, filtered, and concentrated to yield 29.5 g of a crude oil. The crude product was purified by Kugelrohr distillation (0.3°F, 66°C) to yield 13.0 g of 3-(cyclohex-3-en-1-yl)-2-methylacrolein (47.7% yield). Aroma: Spicy, strong, cinnamon, mustard, and basil.

[0206] Example 13: Synthesis of 3-(cyclohex-3-en-1-yl)-2-methylprop-2-en-1-ol

[0207] Example 13 provides the synthesis of a compound of Formula Ia, wherein R1 = R2 = R4 = R5 = H, R3 = methyl, and R6 = cyclohexenyl.

[0208] Under a nitrogen blanket, 3-(cyclohex-3-en-1-yl)-2-methylpropenal (3.9 g, 1 eq.) and 24 mL of methanol were added to a flask and cooled to 5°C. Sodium borohydride (1.6 g, 1.2 eq.) was added and the reaction mixture was stirred at a temperature below 10°C for 2 hours. After this time, the reaction mixture was quenched with water while cooling and the methanol was removed under vacuum. The resulting mixture was extracted with ethyl acetate and concentrated. The crude product was purified by Kugelrohr distillation to give 3.2 g of 3-(cyclohex-3-en-1-yl)-2-methylprop-2-en-1-ol (82.0% yield). Odor: Very strong, lily of the valley, rose, peony, creamy, lactone. GC / MS (EI): m / z (%) 152.1 (M+, 1), 134.1 (2), 121.1 (1), 105.1 (1), 98.1 (7), 97.1 (6), 91.1 (3), 83.1 (7), 80.1 (6), 69.1 (6), 51.1 (1), 43.1 (6). 1H NMR (CDCl3): 5.62-5.70 (m, 2H), 5.30 (dq, J=9.16, 1.37Hz, 1H), 3.99 (d, J=3.66Hz , 2H), 2.43-2.55(m, 1H), 2.02-2.08(m, 3H), 1.60-1.80(m, 4H), 1.32-1.42(m, 2H). 13C NMR (CDCl 3): 133.71, 131.51, 127.02, 126.30, 69.04, 32.45, 31.54, 28.77, 24.81, 13.81.

[0209] Example 14: Synthesis of 3-(cyclohex-3-en-1-yl)-2-methylallyl acetate

[0210] Example 14 provides the synthesis of compounds represented by Formula Ia, wherein R1 = C(O)R7, R2 = R4 = R5 = H, R3 = methyl, R6 = cyclohexenyl, and R7 = methyl.

[0211] Following the same synthetic protocol as in Example 3, 3-(cyclohex-3-en-1-yl)-2-methylprop-2-en-1-ol was substituted for 4-(cyclohex-3-en-1-yl)but-3-en-2-ol. 3-(cyclohex-3-en-1-yl)-2-methylallyl acetate was isolated in a yield of 68.5%. Odor: rose, powdery, fruity, stewed apricot, green, peony. GC / MS (EI): m / z (%) 194(1), 152(5), 134(18), 119(11), 105(7), 91(29), 79(52), 67(11), 53(14), 43(100).

[0212] Example 15: Synthesis of 4-(3-methoxy-2-methylprop-1-en-1-yl)cyclohex-1-ene

[0213] Example 15 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = methyl, R2 = R4 = R5 = H, and R6 = cyclohexenyl.

[0214] The same synthetic protocol as detailed in Example 4 was followed, except that 4-(cyclohex-3-en-1-yl)but-3-en-2-ol was replaced with 3-(cyclohex-3-en-1-yl)-2-methylprop-2-en-1-ol. 4-(3-methoxy-2-methylprop-1-en-1-yl)cyclohex-1-ene was isolated in a yield of 46.1%. Odor: anise, powdery, moldy, cypress, spicy. GC / MS (EI): m / z (%) 166(2), 150(9), 135(30), 121(6), 112(10), 94(29), 80(100), 67(46), 55(51), 45(100).

[0215] Example 16: Synthesis of 4-(cyclohex-3-en-1-yl)-3-methylbut-3-en-2-ol

[0216] Example 16 provides the synthesis of a compound of Formula Ia, wherein R1 = R2 = R5 = H, R3 = R4 = methyl, and R6 = cyclohexenyl.

[0217] The same synthesis scheme as in Example 5 was followed, except that 4-(cyclohex-3-en-1-yl)but-3-en-2-one was replaced with 3-(cyclohex-3-en-1-yl)-2-methylacrolein. 4-(cyclohex-3-en-1-yl)-3-methylbut-3-en-2-ol was isolated in a yield of 66.3%. Odor: floral, aldehyde, lily of the valley. GC / MS (EI): m / z (%) 166.1 (M+, 1), 133.1 (1), 123.1 (1), 112.1 (2), 97.1 (8), 91.1 (2), 85.1 (6), 79.1 (5), 69.1 (6), 55.1 (1), 43.1 (7). 1 HNMR (CDCl3): 5.63-5.70 (m, 2H), 5.29 (d, J=9.16Hz, 1H), 4.18 (q, J=5.95Hz, 1H ), 2.41-2.51(m, 1H), 1.99-2.07(m, 3H), 1.59-1.81(m, 4H), 1.23-1.41(m, 5H). 13C NMR (CDCl3): (mixture of diastereomers) 137.50, 130.41, 130.33, 127.03, 127.00, 126.36, 126.33, 73.48, 73.45, 32.33, 31.55, 31.53, 28.76, 24.82, 21.73, 11.63, 11.55.

[0218] Example 17: Synthesis of 1-(cyclohex-3-en-1-yl)-2-methylpent-1-en-3-ol

[0219] Example 17 provides the synthesis of a compound of Formula Ia, wherein R1 = R2 = R5 = H, R3 = methyl, R4 = ethyl, and R6 = cyclohexenyl.

[0220] Following the same synthetic protocol as in Example 6, 1-(cyclohex-3-en-1-yl)-2-methylpropenal was used in place of 4-(cyclohex-3-en-1-yl)but-3-en-2-one. 1-(cyclohex-3-en-1-yl)-2-methylpent-1-en-3-ol was isolated in a 74.4% yield. Aroma: Floral, petal-like, powdery, balsamic, herbal, woody, spicy, sandalwood, complex. GC / MS (EI): m / z (%) 180 (3), 171 (1), 162 (7), 151 (27), 133 (12), 123 (7), 115 (2), 108 (12), 97 (47), 91 (28), 81 (54), 71 (57), 57 (100), 51 (7), 41 (74). 1H NMR (CDCl3): δ 0.82 (t, 3H), 1.3-1.81 (m, 9H, including a singlet at 3H), 2.04 (m, 3H), 2.47 (broad peak, 1H), 3.87 (t, 1H), 5.25 (d, 1H), 5.65 (m, 2H). 13 C NMR (CDCl3): δ10.0, 11.0, 24.7, 27.6, 27.7, 29.0, 31.4, 79.1, 126.2, 126.3, 126.9, 132.2.

[0221] Example 18: Synthesis of 1-(cyclohex-3-en-1-yl)-2-methylhexyl-1-en-3-ol

[0222] Example 18 provides the synthesis of a compound of Formula Ia, wherein R1 = R2 = R5 = H, R3 = methyl, R4 = propyl, and R6 = cyclohexenyl.

[0223] Following the same synthetic protocol as in Example 9, 4-(cyclohex-3-en-1-yl)but-3-en-2-one was replaced with 3-(cyclohex-3-en-1-yl)-2-methylacrolein. 1-(cyclohex-3-en-1-yl)-2-methylhex-1-en-3-ol was isolated in a yield of 7.7%. GC / MS (EI): m / z (%) 194(2), 176(6), 161(1), 151(13), 133(7), 122(5), 113(20), 105(6), 93(65), 81(47), 71(100), 55(27), 41(62).

[0224] Example 19: Synthesis of 1-(cyclohex-3-en-1-yl)-2-methylhexa-1,5-dien-3-ol

[0225] Example 19 provides the synthesis of a compound of Formula Ia, wherein R1 = R2 = R5 = H, R3 = methyl, R4 = allyl, and R6 = cyclohexenyl.

[0226] Following the same synthetic protocol as in Example 9, 3-(cyclohex-3-en-1-yl)-2-methylacrolein was substituted for 4-(cyclohex-3-en-1-yl)but-3-en-2-one. 1-(cyclohex-3-en-1-yl)-2-methylhexa-1,5-dien-3-ol was isolated in a 9.4% yield. Odor: Solvent, weak.

[0227] Example 20: Synthesis of 3-(cyclohex-3-en-1-yl)-2-methylacrylaldehyde oxime

[0228] Example 20 provides the synthesis of the compound shown in Formula IIa, wherein X = NOH, R2 = R5 = H, R3 = methyl, R6 = cyclohexenyl.

[0229] The same synthetic protocol as detailed in Example 10 was followed, by replacing 4-(cyclohex-3-en-1-yl)but-3-en-2-one with 3-(cyclohex-3-en-1-yl)-2-methylacrolein. 3-(cyclohex-3-en-1-yl)-2-methylacrolein oxime was isolated in a yield of 54.5%. Odor: weak, leathery, mossy. GC / MS (EI): m / z (%) 165.1 (M+, 3), 148.1 (3), 133.1 (1), 110.1 (17), 94.1 (9), 79.1 (5), 67.1 (2), 39.1 (2).

[0230] Example 21: Synthesis of 3-(cyclohex-3-en-1-yl)-2-methylacrolein O-methyloxime

[0231] Example 21 provides the synthesis of a compound of formula IIa, wherein X = NOCH3, R2 = R5 = H, R3 = methyl, and R6 = cyclohexenyl.

[0232] Following the same synthesis protocol as in Example 11, replacing 4-(cyclohex-3-en-1-yl)but-3-en-2-one with 3-(cyclohex-3-en-1-yl)-2-methylacrolein, 3-(cyclohex-3-en-1-yl)-2-methylacrolein O-methyloxime was isolated in a 94.1% yield. Odor: Weak, fruity, violet.

[0233] Example 22: Synthesis of (cyclohex-3-en-1-yl)-2-methylacrylonitrile

[0234] Example 22 provides the synthesis of a compound of formula IIIa, wherein R3 = methyl, R5 = H, and R6 = cyclohexenyl.

[0235] 3-(Cyclohex-3-en-1-yl)-2-methylacrylaldehyde oxime (0.6 g, 1 eq.) was refluxed with 0.06 g of K3PO4 (10 wt% of the oxime) and 6 mL of xylene for 6 hours. After cooling, the reaction mixture was quenched with water and extracted with ether. The crude product was purified by Kugelrohr distillation to give 0.38 g of (cyclohex-3-en-1-yl)-2-methylacrylonitrile (71.7% yield). Odor: Natural honey notes, balsamic, citral, lemon. GC / MS (EI): m / z (%) 179.2 (M+, 20), 164.1 (3), 148.2 (16), 124.1 (58), 110.1 (7), 94.1 (72), 80.1 (42), 67.1 (12), 50.1 (1), 41.1 (10). 1HNMR (CDCl3): 7.63 (s, 1H), 5.64-5.69 (m, 2H), 5.57 (d, J=10.07Hz, 1H), 3.85 (s, 3H), 2.64 -2.69 (m, 1H), 2.05-2.11 (m, 3H), 1.77-1.85 (m, 4H), 1.67-1.71 (m, 1H), 1.36-1.46 (m, 1H). 13 CNMR(CDCl3): 153.67, 143.81, 129.60, 127.07, 125.82, 61.69, 32.99, 30.99, 28.28, 24.50, 11.67.

[0236] Example 23: Synthesis of 2-(cyclohex-3-en-1-ylmethylene)cyclopentane-1-one

[0237] Example 23 provides the synthesis of a compound of formula IIb, wherein n=1, X=O, R2=R3=methyl, R5=H, and R6=cyclohexenyl.

[0238] Cyclohex-3-ene-1-carbaldehyde (20 g, 1 eq.), cyclopentanone (24 mL, 1.5 eq.), NaOH (2.18 g, 0.3 eq.) and water (60 mL) were combined and heated at 35°C for 18 hours. After cooling to room temperature, an additional 100 mL of water was added and the reaction mixture was extracted with ethyl acetate, washed first with 1N HCl and then with brine, dried over MgSO4, filtered and concentrated to 14.4 g of a crude oil. The crude product was purified by Kugelrohr distillation (0.15F, 69°C) to give 8.8 g of 2-(cyclohex-3-en-1-ylmethylene)cyclopentan-1-one (27.5% yield). Odor: dill weed, sour, bright

[0239] Example 24: Synthesis of 2-(cyclohex-3-en-1-ylmethylene)cyclopentan-1-ol

[0240] Example 24 provides the synthesis of a compound of Formula Ib, wherein n=1, R1=R4=R5=H, R2=R3=methyl, and R6=cyclohexenyl.

[0241] The same synthetic protocol as detailed in Example 2 was followed by substituting 2-(cyclohex-3-en-1-ylmethylene)cyclopentan-1-one for 4-(cyclohex-3-en-1-yl)but-3-en-2-one. 2-(cyclohex-3-en-1-ylmethylene)cyclopentan-1-ol was isolated in 74.3% yield. Odor: buttery, mothball, indole, floral. GC / MS (EI): m / z (%) 178(3), 160(24), 145(2), 131(10), 117(16), 106(68), 97(79), 79(200), 67(47), 53(28), 41(52).

[0242] Example 25: Synthesis of 2-(cyclohex-3-en-1-ylmethylene)cyclopentyl acetate

[0243] Example 25 provides the synthesis of a compound of Formula Ib, wherein n=1, R1=C(O)R7, R2=R3=R7=methyl, R4=R5=H, and R6=cyclohexenyl.

[0244] The same synthetic protocol as in Example 3 was followed, by replacing 4-(cyclohex-3-en-1-yl)but-3-en-2-ol with 2-(cyclohex-3-en-1-ylmethylene)cyclopentan-1-ol. 2-(cyclohex-3-en-1-ylmethylene)cyclopentyl acetate was isolated in a yield of 66.6%. Odor: Strong; abundant, citrus, sulfur. GC / MS (EI): m / z (%) 220(1), 178(2), 160(16), 145(3), 131(7), 124(3), 117(18), 106(73), 97(39), 91(83), 79(100), 67(41), 53(27), 43(72).

[0245] Example 26: Synthesis of 4-((2-methoxycyclopentylidene)methyl)cyclohex-1-ene

[0246] Example 26 provides the synthesis of a compound of Formula Ib, wherein n=1, R1=R2=R3=methyl, R4=R5=H, and R6=cyclohexenyl.

[0247] The same synthesis protocol as in Example 4 was followed, substituting 2-(cyclohex-3-en-1-ylmethylene)cyclopentan-1-ol for 4-(cyclohex-3-en-1-yl)but-3-en-2-ol. 4-((2-methoxycyclopentylidene)methyl)cyclohex-1-ene was isolated in a 68.2% yield. Odor: Onion, gaseous.

[0248] Example 27: Synthesis of 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-one

[0249] Example 27 provides the synthesis of a compound of formula IIa, wherein X = O, R2 = methyl, R3 = R5 = H, and R6 = bicyclo[2.2.1]hept-5-enyl.

[0250] Following the same synthetic protocol as detailed in Example 1, replacing cyclohex-3-ene-1-carbaldehyde with bicyclo[2.2.1]hept-5-ene-2-carbaldehyde, 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-one was isolated in 47.7% yield. Odor: Pungent, spicy aroma.

[0251] Example 28: Synthesis of 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-ol

[0252] Example 28 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R4 = R5 = H, R2 = methyl, and R6 = bicyclo[2.2.1]hept-5-enyl.

[0253] The same synthetic protocol as detailed in Example 2 was followed by replacing 4-(cyclohex-3-en-1-yl)but-3-en-2-one with 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-ol. 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-ol was isolated in a yield of 68.0%. Odor: slightly floral, rotten cucumber, fruity. GC / MS (EI): m / z (%) 164(1), 148(2), 131(3), 120(5), 115(3), 105(5), 95(6), 91(20), 79(28), 66(100), 53(14), 45(7), 41(31).

[0254] Example 29: Synthesis of 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-yl acetate

[0255] Example 29 provides the synthesis of compounds of Formula Ia, wherein R1 = C(O)R7, R2 = R7 = methyl, R3 = R4 = R5 = H and R6 = bicyclo[2.2.1]hept-5-enyl.

[0256] The same synthetic protocol as detailed in Example 3 was followed by substituting 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-ol for 4-(cyclohex-3-en-1-yl)but-3-en-2-ol. 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-yl acetate was isolated in a yield of 66.6%. Odor: wet dog, woody, marine, seaside. GC / MS (EI): m / z (%) 191 (M+-15, 1), 146 (8), 140 (6), 131 (8), 117 (6), 105 (3, 98 (8)), 91 (12), 81 (26), 66 (65), 53 (10), 43 (100).

[0257] Example 30: Synthesis of 5-(3-methoxybut-1-en-1-yl)bicyclo[2.2.1]hept-2-ene

[0258] Example 30 provides the synthesis of a compound of Formula Ia, wherein R1 = R2 = methyl, R3 = R4 = R5 = H, and R6 = bicyclo[2.2.1]hept-5-enyl.

[0259] The same synthetic protocol as detailed in Example 4 was followed by replacing 4-(cyclohex-3-en-1-yl)but-3-en-2-ol with 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-ol. 5-(3-methoxybut-1-en-1-yl)bicyclo[2.2.1]hept-2-ene was isolated in 71.3% yield. Odor: weak, violet. GC / MS (EI): m / z (%) 178(1), 163(1), 146(5), 131(4), 117(5), 111(11), 105(3), 97(58), 91(14), 81(60), 66(100), 59(43), 53(16), 41(34).

[0260] Example 31: Synthesis of 4-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylbut-3-en-2-ol

[0261] Example 31 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = R4 = methyl, and R6 = bicyclo[2.2.1]hept-5-enyl.

[0262] The same synthetic protocol as in Example 5 was followed, by replacing 4-(cyclohex-3-en-1-yl)but-3-en-2-one with 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-one. 4-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylbut-3-en-2-ol was isolated in a yield of 30.3%. Odor: weak, violet, lily of the valley. GC / MS (EI): m / z (%) 178(1), 160(3), 145(2), 128(1), 117(6), 111(1), 105(4), 95(36), 79(37), 66(100), 59(18), 53(16), 41(72).

[0263] Example 32: Synthesis of 1-(bicyclo[2.2.1]hept-5-en-2-yl)-3-methylpent-1-en-3-ol

[0264] Example 32 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = ethyl, and R6 = bicyclo[2.2.1]hept-5-enyl.

[0265] Following the same synthetic protocol as detailed in Example 6, by replacing 4-(cyclohex-3-en-1-yl)but-3-en-2-one with 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-one, 1-(bicyclo[2.2.1]hept-5-en-2-yl)-3-methylpent-1-en-3-ol was isolated in 50.0% yield. Odor: wet hair, woody, sweaty, fig, winey, fruity, smooth, violet, lily of the valley, floral, apple, buttery, creamy. GC / MS (EI): m / z (%) 192(1), 163(1), 145(1), 120(3), 91(15), 66(100), 43(67).

[0266] Example 33: Synthesis of 1-(bicyclo[2.2.1]hept-5-en-2-yl)-3-methylpenta-1,4-dien-3-ol

[0267] Example 33 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = vinyl, and R6 = bicyclo[2.2.1]hept-5-enyl.

[0268] Following the same synthetic protocol as in Example 7, 4-(cyclohex-3-en-1-yl)but-3-en-2-one was substituted with 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-one. 1-(bicyclo[2.2.1]hept-5-en-2-yl)-3-methylpenta-1,4-dien-3-ol was isolated in a yield of 12.5%. GC / MS (EI): m / z (%) 190(1), 174(3), 157(2), 148(1), 143(2), 129(4), 120(2), 115(7), 108(26), 93(100), 79(59), 71(8), 66(90), 53(25), 43(67).

[0269] Example 34: Synthesis of 1-(bicyclo[2.2.1]hept-5-en-2-yl)-3,4-dimethylpent-1-en-3-ol

[0270] Example 34 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = isopropyl, and R6 = bicyclo[2.2.1]hept-5-enyl.

[0271] Following the same synthetic protocol as detailed in Example 8, replacing 4-(cyclohex-3-en-1-yl)but-3-en-2-one with 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-one, 1-(bicyclo[2.2.1]hept-5-en-2-yl)-3,4-dimethylpent-1-en-3-ol was isolated in a 50.0% yield. Aroma: dill, blueberry, sour, medicinal.

[0272] Example 35: Synthesis of 1-(bicyclo[2.2.1]hept-5-en-2-yl)-3-methylhexen-1-en-3-ol

[0273] Example 35 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = propyl, and R6 = bicyclo[2.2.1]hept-5-enyl.

[0274] Following the same synthetic protocol as detailed in Example 9, replacing 4-(cyclohex-3-en-1-yl)but-3-en-2-one with 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-one, 1-(bicyclo[2.2.1]hept-5-en-2-yl)-3-methylpenta-1,4-dien-3-ol was isolated in a 44.1% yield. Aroma: Delicious, rosemary, sage, dill, complex, mossy, violet. GC / MS(EI): m / z(%)206(1), 188(1), 163(1), 148(3), 141(4), 133(1), 127(5), 1 19(2), 111(1), 105(2), 97(4), 91(6), 83(4), 77(6), 66(100), 55(10), 43(71).

[0275] Example 36: Synthesis of 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-one O-methyloxime

[0276] Example 36 provides the synthesis of a compound of formula IIa, wherein X = NOCH3, R2 = methyl, R3 = R5 = H, and R6 = bicyclo[2.2.1]hept-5-enyl.

[0277] Following the same synthetic protocol as detailed in Example 11, replacing 4-(cyclohex-3-en-1-yl)but-3-en-2-one with 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-one, 4-(bicyclo[2.2.1]hept-5-en-2-yl)but-3-en-2-one O-methyloxime was isolated in a 66.1% yield. Aroma: milky, phytoanthus, lily of the valley. GC / MS (EI): m / z (%) 191 (1), 176 (1), 161 (4), 146 (3), 141 (4), 137 (3), 124 (70), 115 (14), 105 (6), 94 (100), 77 (35), 66 (48), 53 (31), 42 (60).

[0278] Example 37: Synthesis of 3-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylacrolein

[0279] Example 37 provides the synthesis of a compound of Formula IIa, wherein X = O, R2 = R5 = H, R3 = methyl, and R6 = bicyclo[2.2.1]hept-5-enyl.

[0280] The same synthetic protocol as detailed in Example 12 was followed, substituting bicyclo[2.2.1]hept-5-ene-2-carbaldehyde for cyclohex-3-ene-1-carbaldehyde. 3-(Bicyclo[2.2.1]hept-5-en-2-yl)-2-methylacrolein was isolated in 63.1% yield as a mixture of two major isomers. Odor: Pungent, chemical, cheesy. 1 H NMR (CDCl3): δ 9.27 and 9.36 (singlet, 1H aldehyde peak), 1.76 and 1.77 (singlet, 3H methyl peak) 13 C NMR (CDCl3): δ 195.2 and 195.4 (aldehyde peak).

[0281] Example 38: Synthesis of 3-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylprop-2-en-1-ol

[0282] Example 38 provides the synthesis of a compound of Formula Ia, wherein R1 = R2 = R4 = R5 = H, R3 = methyl, and R6 = bicyclo[2.2.1]hept-5-enyl.

[0283] The same synthetic protocol as detailed in Example 13 was followed by replacing 3-(cyclohex-3-en-1-yl)-2-methylacrolein with 3-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylprop-2-en-1-ol. 3-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylprop-2-en-1-ol was isolated in a yield of 56.15%. Odor: green, chemical, grassy, ​​vegetative. GC / MS (EI): m / z (%) 164(1), 149(8), 138(100), 123(4), 101(4), 85(25), 73(98), 55(14), 41(27).

[0284] Example 39: Synthesis of 3-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylallyl acetate

[0285] Example 39 provides the synthesis of compounds of Formula Ia, wherein R1 = C(O)R7, R2 = R4 = R5 = H, R3 = methyl, R6 = bicyclo[2.2.1]hept-5-enyl, and R7 = methyl.

[0286] Following the same synthetic protocol as described in Example 14, 3-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylprop-2-en-1-ol was substituted for 4-(cyclohex-3-en-1-yl)but-3-en-2-ol. 3-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylallyl acetate was isolated in a 28.0% yield. Aroma: Gourmet, lactonic, buttery, milky, sweet.

[0287] Example 40: Synthesis of 4-cyclohexylbut-3-en-2-one

[0288] Example 40 provides the synthesis of a compound of formula IIa, wherein X = O, R2 = methyl, R3 = R5 = H, and R6 = cyclohexyl.

[0289] Following the same synthesis protocol as in Example 1, cyclohexanecarboxaldehyde was substituted for cyclohex-3-ene-1-carboxaldehyde. 4-Cyclohexylbut-3-ene-2-one was isolated in a yield of 65.8%. Aroma: balsamic, herbal, peppery, cumin, pine. GC / MS (EI): m / z (%) 152 (20), 137 (6), 119 (3), 109 (23), 94 (40), 79 (28), 67 (61), 55 (76), 43 (100).

[0290] Example 41: Synthesis of 4-cyclohexylbut-3-en-2-ol

[0291] Example 41 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R4 = R5 = H, R2 = methyl, and R6 = cyclohexyl.

[0292] The same synthetic protocol as detailed in Example 2 was followed, substituting 4-cyclohexylbut-3-en-2-one for 4-(cyclohex-3-en-1-yl)but-3-en-2-one. 4-Cyclohexylbut-3-en-2-ol was isolated in a yield of 56.4%. Odor: herbal, sweet, creamy, oily, paint-like. GC / MS (EI): m / z (%) 154(1), 136(30), 121(20), 107(33), 99(27), 94(29), 83(17), 79(76), 71(100), 67(79), 55(75), 41(86).

[0293] Example 42: Synthesis of 4-cyclohexylbut-3-en-2-yl acetate

[0294] Example 42 provides the synthesis of a compound of Formula Ia, wherein R1 = C(O)R7, R2 = R7 = methyl, R3 = R4 = R5 = H, and R6 = cyclohexyl.

[0295] The same synthetic protocol as detailed in Example 3 was followed, substituting 4-cyclohexylbut-3-en-2-ol for 4-(cyclohex-3-en-1-yl)but-3-en-2-ol. 4-Cyclohexylbut-3-en-2-yl acetate was obtained in 67.7% yield. Odor: Pleasant, similar to linalool acetate, citrus. GC / MS (EI): m / z (%) 196(1), 181(1), 154(7), 136(18), 121(6), 113(4), 107(20), 99(4), 93(10), 79(35), 67(32), 55(25), 43(100).

[0296] Example 43: Synthesis of (3-methoxybut-1-en-1-yl)cyclohexane

[0297] Example 43 provides the synthesis of a compound of Formula Ia, wherein R1 = R2 = methyl, R3 = R4 = R5 = H and R6 = cyclohexyl.

[0298] The same synthetic protocol as detailed in Example 4 was followed, substituting 4-cyclohexylbut-3-en-2-ol for 4-(cyclohex-3-en-1-yl)but-3-en-2-ol. (3-Methoxybut-1-en-1-yl)cyclohexane was isolated in 55.0% yield. Odor: rotten, garbage. GC / MS (EI): m / z (%) 168(1), 153(3), 136(5), 121(4), 113(4), 107(6), 97(2), 93(7), 85(100), 79(28), 71(58), 67(24), 59(30), 55(40), 41(45).

[0299] Example 44: Synthesis of 4-cyclohexyl-2-methylbut-3-en-2-ol

[0300] Example 44 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = R4 = methyl, and R6 = cyclohexyl.

[0301] The same synthetic protocol as detailed in Example 5 was followed, substituting 4-cyclohexylbut-3-en-2-one for 4-(cyclohex-3-en-1-yl)but-3-en-2-one. 4-Cyclohexyl-2-methylbut-3-en-2-ol was isolated in 49.0% yield. Odor: freesia, lily of the valley, linalool-like. GC / MS (EI): m / z (%) 168(1), 150(14), 135(18), 121(3), 107(15), 99(16), 93(25), 85(39), 79(42), 71(100), 67(56), 59(25), 55(36), 41(83).

[0302] Example 45: Synthesis of 1-cyclohexyl-3-methylpent-1-en-3-ol

[0303] Example 45 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = ethyl, and R6 = cyclohexyl.

[0304] The same synthetic protocol as in Example 6 was followed, substituting 4-cyclohexylbut-3-en-2-one for 4-(cyclohex-3-en-1-yl)but-3-en-2-one. 1-Cyclohexyl-3-methylpent-1-en-3-ol was isolated in a yield of 52.1%. Odor: pleasant, floral. GC / MS (EI): m / z (%) 182(1), 164(8), 153(17), 135(20), 121(3), 107(11), 99(5), 93(22), 85(8), 79(26), 71(100), 67(38), 55(35), 41(50).

[0305] Example 46: Synthesis of 1-cyclohexyl-3,4-dimethylpent-1-en-3-ol

[0306] Example 46 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = isopropyl, and R6 = cyclohexyl.

[0307] The same synthetic protocol as detailed in Example 8 was followed, substituting 4-cyclohexylbut-3-en-2-one for 4-(cyclohex-3-en-1-yl)but-3-en-2-one. 1-Cyclohexyl-3,4-dimethylpent-1-en-3-ol was isolated in 50.0% yield. Odor: weak floral. GC / MS (EI): m / z (%) 178 (M+-18, 4), 163 (3), 153 (10), 135 (10), 121 (3), 115 (1, 107 (10)), 91 (20), 79 (24), 71 (40), 67 (25), 55 (53), 41 (100).

[0308] Example 47: Synthesis of 1-cyclohexyl-3-methylhexyl-1-en-3-ol

[0309] Example 47 provides the synthesis of a compound of Formula Ia, wherein R1 = R3 = R5 = H, R2 = methyl, R4 = propyl, and R6 = cyclohexyl.

[0310] The same synthetic protocol as detailed in Example 9 was followed, substituting 4-cyclohexylbut-3-en-2-one for 4-(cyclohex-3-en-1-yl)but-3-en-2-one. 1-Cyclohexyl-3-methylhex-1-en-3-ol was isolated in 33.0% yield. Odor: fatty, aldehyde, floral. GC / MS (EI): m / z (%) 178 (M+-18, 10), 163 (1), 153 (17), 135 (19), 121 (3), 113 (3), 107 (16)), 99 (6), 93 (31), 81 (51), 71 (100), 67 (43), 55 (60), 41 (80).

[0311] Example 48: Synthesis of 4-cyclohexylbut-3-ene-2-one oxime

[0312] Example 48 provides the synthesis of a compound of formula IIa, wherein X = NOH, R2 = methyl, R3 = R5 = H, and R6 = cyclohexyl.

[0313] The same synthetic protocol as detailed in Example 10 was followed, substituting 4-cyclohexylbut-3-en-2-one for 4-(cyclohex-3-en-1-yl)but-3-en-2-one. 4-Cyclohexylbut-3-en-2-one oxime was isolated in a yield of 3.2%. Odor: pungent, chemical. GC / MS (EI): m / z (%) 167(6), 150(1), 136(1), 122(1), 108(3), 98(1), 94(6), 84(61), 79(12), 71(2), 67(27), 55(98), 41(100).

[0314] Example 49: Synthesis of 4-cyclohexylbut-3-en-2-one O-methyloxime

[0315] Example 49 provides the synthesis of a compound of formula IIa, wherein X = NOCH3, R2 = methyl, R3 = R5 = H, and R6 = cyclohexyl.

[0316] The same synthetic protocol as detailed in Example 11 was followed, substituting 4-(cyclohex-3-en-1-yl)but-3-en-2-one for 4-cyclohexylbut-3-en-2-one. 4-Cyclohexylbut-3-en-2-one O-methyloxime was isolated in a yield of 50.4%. Odor: chemical, weak. GC / MS (EI): m / z (%) 181 (24), 166 (16), 150 (42), 138 (13), 124 (28), 108 (16), 94 (47), 79 (34), 71 (2), 67 (53), 55 (43), 41 (100).

[0317] Example 50: Synthesis of 3-cyclohexyl-2-methylacrolein

[0318] Example 50 provides the synthesis of a compound of formula IIa, wherein X = O, R2 = R5 = H, R3 = methyl, and R6 = cyclohexyl.

[0319] The same synthetic protocol as detailed in Example 12 was followed, substituting cyclohexanecarboxaldehyde for cyclohex-3-ene-1-carboxaldehyde. 3-Cyclohexyl-2-methylacrolein was isolated in a yield of 42.8%. Odor: solvent, paint-like. GC / MS (EI): m / z (%) 152 (49), 137 (9), 123 (13), 109 (28), 95 (43), 81 (64), 67 (100), 55 (42), 41 (83).

[0320] Example 51: Synthesis of 3-cyclohexyl-2-methylprop-2-en-1-ol

[0321] Example 51 provides the synthesis of a compound of Formula Ia, wherein R1 = R2 = R4 = R5 = H, R3 = methyl, and R6 = cyclohexyl.

[0322] The same synthetic protocol as detailed in Example 13 was followed, substituting 3-cyclohexyl-2-methylacrolein for 3-(cyclohex-3-en-1-yl)-2-methylacrolein. 3-Cyclohexyl-2-methylprop-2-en-1-ol was isolated in a 69.2% yield. Aroma: licorice, blueberry, red fruit, floral, green, rose. GC / MS (EI): m / z (%) 154(3), 136(2), 123(19), 99(100), 81(79), 67(52), 55(60), 41(61).

[0323] Example 52: Synthesis of 3-cyclohexyl-2-methylallyl acetate

[0324] Example 52 provides the synthesis of a compound of Formula Ia, wherein R1 = C(O)R7, R2 = R4 = R5 = H, R3 = R7 = methyl, and R6 = cyclohexyl.

[0325] The same synthesis scheme as in Example 3 was followed, substituting 3-cyclohexyl-2-methylprop-2-en-1-ol for 4-(cyclohex-3-en-1-yl)but-3-en-2-ol. 3-Cyclohexyl-2-methylallyl acetate was isolated in a yield of 68.5%. Odor: Herbal, musty, dill-like. GC / MS (EI): m / z (%) 196(1), 165(1), 154(6), 136(59), 121(84), 107(18), 93(30), 81(53), 67(33), 55(34), 41(100).

[0326] Example 53: Synthesis of 3-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylacrylaldehyde oxime

[0327] Example 53 provides the synthesis of a compound of Formula IIa, wherein X = NOH, R2 = R5 = H, R3 = methyl, and R6 = bicyclo[2.2.1]hept-5-enyl.

[0328] Following the same synthetic protocol as detailed in Example 10, 3-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylacrolein was substituted for 4-(cyclohex-3-en-1-yl)but-3-en-2-one. 3-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylacrolein oxime was isolated in a 54.4% yield. Odor: Earthy, soily, dusty, fruity.

[0329] Example 54: Synthesis of 3-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylacrylonitrile

[0330] Example 54 provides the synthesis of a compound of formula IIIa, wherein R3 = methyl, R5 = H, and R6 = bicyclo[2.2.1]hept-5-enyl.

[0331] The same synthetic protocol as detailed in Example 22 was followed, substituting 3-(cyclohex-3-en-1-yl)-2-methylpropenaldoxime for 3-(bicyclo[2.2.1]hept-5-en-2-yl)-2-methylpropenaldoxime. 3-(Bicyclo[2.2.1]hept-5-en-2-yl)-2-methylpropenonitrile was isolated in a 6.8% yield. Odor: solvent, banana, citrus, green, floral, sour. GC / MS (EI): m / z (%) 159(11), 144(15), 131(10), 117(32), 105(18), 91(21), 77(15), 66(100), 51(17), 39(40).

[0332] Example 55: Synthesis of 3-cyclohexyl-2-methylacrylaldehyde oxime

[0333] Example 55 provides the synthesis of a compound represented by Formula IIa, wherein X = NOH, R2 = R5 = H, R3 = methyl, and R6 = cyclohexyl.

[0334] The same synthetic protocol as detailed in Example 10 was followed, substituting 3-cyclohexyl-2-methylpropenal for 4-(cyclohex-3-en-1-yl)but-3-en-2-one. 3-Cyclohexyl-2-methylpropenal oxime was isolated in a yield of 72.1%. Odor: green, musty, vegetative. GC / MS (EI): m / z (%) 167 (68), 150 (100), 135 (6), 124 (75), 110 (72), 94 (53), 81 (34), 67 (70), 55 (37), 41 (78).

[0335] Example 56: Synthesis of 3-cyclohexyl-2-methacrylonitrile

[0336] Example 56 provides the synthesis of a compound of formula IIIa, wherein R3 = methyl, R5 = H, and R6 = cyclohexyl.

[0337] The same synthesis protocol as in Example 22 was followed, substituting 3-cyclohexyl-2-methylpropenaldoxime for 3-(cyclohex-3-en-1-yl)-2-methylpropenaldoxime. 3-Cyclohexyl-2-methylacrylonitrile was isolated in a 57.7% yield. Odor: sweet, plum, liquorice, herbal. GC / MS (EI): m / z (%) 149(4), 134(5), 120(5), 106(10), 93(11), 82(49), 67(100), 54(23), 41(42).

[0338] Example 57: Perfume composition for liquid detergent

[0339] The compound of Example 3 was used to prepare a ginger mangosteen fragrance composition for demonstration in a liquid detergent. The compound of Example 3 was used at a 10% dilution in DPG. Table 1 provides the composition.

[0340] Table 1

[0341]

[0342] Comparative fragrance compositions were prepared in which DPG was substituted for the compound of Example 3. Table 2 provides the comparative fragrance compositions.

[0343] Table 2

[0344]

[0345]

[0346] A second comparative fragrance composition was prepared using trans-2-dodecenal (10% / TEC) in place of the compound of Example 3. Table 3 provides the second comparative fragrance composition.

[0347] Table 3

[0348]

[0349] Each fragrance composition was dosed at 0.7% in a commercial liquid detergent base and evaluated by five experts in the field of fragrance evaluation. Compared to the version containing DPG, the composition using the compound of Example 3 was juicier, softer, and less greasy than the composition containing trans-2-dodecenal, and had stronger efficacy with a sparkling citrus note.

[0350] Example 58: Perfume composition for use in shampoo

[0351] A citrus fragrance composition was prepared from the compound of Example 3 for demonstration in a shampoo. The compound of Example 3 was used at a 10% dilution in DPG. Table 4 provides the composition of the fragrance.

[0352] Table 4

[0353]

[0354] Comparative fragrance compositions were prepared in which DPG was substituted for the compound of Example 3. Table 5 provides the comparative fragrance compositions.

[0355] Table 5

[0356]

[0357]

[0358] A second comparative fragrance composition was prepared using trans-2-dodecenal (10% / DPG) in place of the compound of Example 3. Table 6 provides the second comparative fragrance composition.

[0359] Table 6

[0360]

[0361] Each fragrance composition was dosed at 0.8% in a commercial shampoo base and evaluated by five experts in the field of fragrance evaluation. The composition using the compound of Example 3 gave a cleaner and more complex citrus fragrance than the version with trans-2-dodecenal, and added greater volume and citrus aroma than the version with DPG.

[0362] Example 59: Perfume composition for use in shampoo

[0363] A passion fruit type fragrance composition was prepared from the compound of Example 3 for demonstration in shampoo. The compound of Example 3 was used at a 10% dilution in DPG. Table 7 provides the composition of the fragrance.

[0364] Table 7

[0365]

[0366] Comparative fragrance compositions were prepared in which DPG was substituted for the compound of Example 3. Table 8 provides the comparative fragrance compositions.

[0367] Table 8

[0368] Spice categories Parts per thousand Wt.% Citrus 121.0 12.1 Floral scent 283.0 28.3 fruity 384.0 38.4 Delicious food 5.0 0.5 Qingxiang 21.5 2.1 Musk 35.0 3.5 Woody and / or ambery notes 0.5 0.1 Solvent (DPG) 150 15.0 total 1000 100

[0369] A second comparative fragrance composition was prepared using trans-2-dodecenal (10% / DPG) in place of the compound of Example 3. Table 9 provides the second comparative fragrance composition.

[0370] Table 9

[0371]

[0372] Each fragrance composition was dosed at 0.8% in a commercial shampoo base and evaluated by five experts in the field of fragrance evaluation. Compared to the version with trans-2-dodecenal, the composition using the compound of Example 3 gave a more authentic tropical fruit fragrance without a greasy feel, and had a more natural passion fruit character than the version with DPG.

[0373] Example 60: Fragrance Composition for Liquid Electric Air Freshener

[0374] A fragrance composition for a liquid electric air freshener was prepared using the compound of Example 17. The fragrance composition is provided in Table 10.

[0375] Table 10

[0376]

[0377]

[0378] Comparative fragrance compositions were prepared in which DPG was substituted for the compound of Example 17. Table 11 provides the comparative fragrance compositions.

[0379] Table 11

[0380]

[0381] Fragrance compositions containing and without the compound of Example 17 were evaluated by two experts in the field of fragrance evaluation. Compared to compositions without the compound of Example 17, compositions containing the compound of Example 17 were found to add a rich, balsamic, powdery fragrance. Furthermore, the compound of Example 17 was found to increase the amount of makeup that filled a room. The inclusion of the compound of Example 17 did not affect the weight loss of the fragrance in the liquid electric device.

[0382] Example 61: Fragrance composition

[0383] A fragrance composition was prepared from the compound of Example 3. The fragrance composition is provided in Table 12.

[0384] Table 12

[0385] Fragrance compounds Wt.% Compound of Example 3 0.010 Propylene glycol 98.745 Flavor Actives 1.245 total 100

[0386] Comparative fragrance compositions were prepared in which propylene glycol was substituted for the compound of Example 3. Table 13 provides the comparative fragrance compositions.

[0387] Table 13

[0388] Fragrance compounds Wt.% Propylene glycol 98.755 Flavor Actives 1.245 total 100

[0389] 0.1% flavor, 5.0% sugar, and 0.1% citric acid were added to water and then evaluated by three flavor experts. The evaluators determined that the composition containing the compound of Example 3 had more fleshy and juicy characteristics than the control and was more reminiscent of natural grapefruit.

[0390] ***

[0391] Although the disclosed subject matter and its advantages have been described in detail, it should be understood that various changes, substitutions and modifications can be made herein without departing from the spirit and scope of the disclosed subject matter as defined by the appended claims. In addition, the scope of this application is not intended to be limited to the specific embodiments of the processes, devices, manufacturing methods, material compositions, modes, methods and steps described in the specification. As one of ordinary skill in the art will understand from the disclosure of the disclosed subject matter, processes, devices, manufacturing methods, material compositions, modes, methods or steps, currently existing or later developed content can be used in accordance with the disclosed subject matter, which have substantially the same functions as the corresponding embodiments described herein or can achieve substantially the same effects. Therefore, the appended claims are intended to include such processes, devices, manufacturing methods, material compositions, modes, methods or steps within their scope.

[0392] In addition to the various embodiments depicted and claimed, the disclosed subject matter is also directed to other embodiments having any other possible combination of the features disclosed and claimed herein. Thus, the specific features presented herein can be combined with each other in other ways within the scope of the disclosed subject matter, such that the disclosed subject matter includes any suitable combination of the features disclosed herein. Therefore, the foregoing description of specific embodiments of the disclosed subject matter has been presented for purposes of illustration and description, and is not intended to be exhaustive or to limit the disclosed subject matter to those disclosed embodiments.

[0393] It will be apparent to those skilled in the art that various modifications and variations can be made to the apparatus, method, and system of the disclosed subject matter without departing from the spirit or scope of the disclosed subject matter. Therefore, the disclosed subject matter is intended to include modifications and variations within the scope of the appended claims and their equivalents.

[0394] For any patents, patent applications, publications, product descriptions, and protocols cited throughout this application, the entire disclosures of these are incorporated herein by reference in their entirety for all purposes.

Claims

1. A flavor or fragrance compound for use in a flavor or fragrance having the formula wherein R1 is C(O)R7; wherein R2 is H; wherein R3 is methyl; wherein R4 is H; wherein R5 is H; and wherein R7 is methyl, or wherein R1 is C(O)R7; wherein R2 is methyl; wherein R3 is H; wherein R4 is H; wherein R5 is H; and wherein R7 is methyl.

2. A flavor or fragrance composition comprising one or more flavor or fragrance compounds according to claim 1.

3. The flavor composition of claim 2, wherein the concentration of the one or more flavor compounds is from 0.01% to 20% by weight of the flavor composition.

4. The fragrance composition of claim 2, further comprising one or more additional compounds selected from the group consisting of one or more aldehyde compounds, one or more meaty compounds, one or more balsamic compounds, one or more citrus compounds, one or more floral compounds, one or more fruity compounds, one or more gourmand compounds, one or more green compounds, one or more herbal compounds, one or more marine compounds, one or more mossy compounds, one or more musk compounds, one or more pine compounds, one or more powdery compounds, one or more spicy compounds and / or one or more woody and / or ambery compounds, and combinations thereof.

5. The fragrance composition of claim 2, wherein the concentration of the one or more fragrance compounds is from 0.001% to 20% by weight of the fragrance composition. The fragrance composition of claim 5 , further comprising a fragrance carrier.

7. A consumer product comprising one or more compounds of claim 1 or a composition of claim 2.

8. The flavor or fragrance compound for use in flavors or fragrances according to claim 1, wherein R1 is C(O)R7; wherein R2 is methyl; wherein R3 is H; wherein R4 is H; wherein R5 is H; and wherein R7 is methyl.

9. The flavor or fragrance compound for use in flavors or fragrances according to claim 1, wherein R1 is C(O)R7; wherein R2 is H; wherein R3 is methyl; wherein R4 is H; wherein R5 is H; and wherein R7 is methyl.

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