Unsaturated ether perfume precursors

Abstract

There is provided the use of a compound of formula (I) as a perfume precursor capable of releasing a perfume having an aldehyde scent. Also provided are perfume compositions and consumer products comprising the compounds, as well as the compounds themselves.

Description

Technical Field

[0001] This invention generally relates to fragrance precursors capable of releasing aromatic compounds. It also relates to fragrance formulations and consumer products containing said precursors. Furthermore, it relates to methods for preparing said fragrance precursors, fragrance formulations, and consumer products, and the use of said fragrance precursors and fragrance formulations in consumer products such as personal care and home care products.

[0002] background

[0003] Fragrance-enhanced consumer products, such as cleaning or laundry products containing fragrances, are well known in the art. However, fragrances are known to be altered by degradation caused by interaction with air or when incorporated into certain consumer product bases, where the presence of alkaline, acidic, oxidizing agents such as hypochlorites, or other base components can lead to chemical degradation of the fragrance. Furthermore, volatile fragrances tend to dissipate over time. Additionally, when used in cleaning or laundry products, washing and / or rinsing processes reduce the deposition of fragrances on treated substrates.

[0004] However, consumers expect products that can be stored over time and still provide a consistent fragrance impression. In particular, the effects of volatile components should be preserved. Furthermore, such products are expected to produce a long-lasting, pleasant fragrance that slowly diffuses from the treated substrate over time.

[0005] To meet these needs, flavor precursors can be used, which are substances that are essentially odorless in themselves, but under certain conditions, the flavor precursors will decompose to release aromatic molecules.

[0006] Several classes of known precursors release aromatic molecules upon activation (e.g., hydrolysis, temperature change, oxygen, light, and enzymatic action). For example, WO2012085287 reports a group of precursors capable of releasing fragrances via spontaneous air oxidation. Another group of precursors that can be cleaved by hydrolysis is described in WO2007143873.

[0007] Typically, precursors do exhibit varying degrees of stability, and they release aromatic molecules under different conditions. For example, there remains a need to provide further precursor systems to improve fragrance effects on dry fabrics after several days. Therefore, there is a desire to provide a new or improved system capable of releasing fragrance over extended periods and providing a sustained fragrance release.

[0008] Overview

[0009] According to a first aspect of the invention, there is provided the use of a compound as a fragrance precursor, which is capable of releasing fragrance over an extended period of time and providing a sustained release of said fragrance.

[0010] According to a second aspect of the invention, a compound is provided as a precursor.

[0011] According to a third aspect of the invention, a method for releasing fragrance is provided.

[0012] According to a fourth aspect of the present invention, a method for preparing the fragrance precursor, fragrance formulation, and consumer product is provided.

[0013] According to a fifth aspect of the invention, fragrance formulations and consumer products comprising the said compound are provided.

[0014] According to a sixth aspect of the invention, the use of the fragrance precursor and fragrance formulation in consumer products such as fabric care, personal care and home care products is provided.

[0015] Details, embodiments, and preferred embodiments provided with respect to any particular aspect or one of the described aspects of the invention will be further described herein, and are equally applicable to all aspects of the invention. Unless otherwise stated herein or obviously contradicted by the context, any combination of all possible variations of the embodiments, embodiments, and preferred embodiments described herein is included in the invention.

[0016] Detailed description

[0017] This invention is based on the surprising discovery that simple allyl esters, carbonates, carbamates, and sulfonates can be used as fragrance precursors capable of releasing fragrance. These fragrance precursors provide delayed fragrance release over a longer period compared to using the fragrance compound itself.

[0018] Therefore, this article provides the use of compounds of formula (I) as fragrance precursors.

[0019]

[0020] in

[0021] X is selected from C and S (=O);

[0022] R1 is selected from straight chains or branched chains C1-C. 11 Alkyl; methoxy; ethoxy; phenyl having up to five independent substituents selected from methyl, ethyl, methoxy, ethoxy; naphthyl having up to four independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-naphthyl-methyl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-(2-naphthyl)-ethyl-1-yl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; dialkylamine-NR5R6, wherein R5 and R6 are independently selected from C1-C4 alkyl groups;

[0023] R2 is selected from the straight chain C7-C.10 Alkyl groups and straight-chain C7-C bonds with terminal C-C double bonds 10 alkenyl;

[0024] R3 is selected from H, Me, Et, phenyl, 2-naphthyl, 4-methoxyphenyl; and

[0025] R4 is selected from H and Me.

[0026] For example, the use of a compound of formula (I) as a flavoring precursor is provided, wherein the compound is a compound of formula (Ia).

[0027]

[0028] in

[0029] R1 is selected from straight chains or branched chains C1-C. 11 Alkyl; methoxy; ethoxy; phenyl having up to five independent substituents selected from methyl, ethyl, methoxy, ethoxy; naphthyl having up to four independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-naphthyl-methyl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-(2-naphthyl)-ethyl-1-yl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; dialkylamine-NR5R6, wherein R5 and R6 are independently selected from C1-C4 alkyl groups;

[0030] R2 is selected from the straight chain C7-C. 10 Alkyl groups and straight-chain C7-C bonds with terminal C-C double bonds 10 alkenyl;

[0031] R3 is selected from H, Me, Et, phenyl, 2-naphthyl, 4-methoxyphenyl; and

[0032] R4 is selected from H and Me.

[0033] Compound (Ia) corresponds to compound (I) in which X is C. Compound (Ia) includes homoallyl esters, carbonates, and carbamates.

[0034] For example, the use of a compound of formula (I) as a flavoring precursor is provided, wherein said compound is a compound of formula (Ib).

[0035]

[0036] in

[0037] R1 is selected from straight chains or branched chains C1-C. 11Alkyl; methoxy; ethoxy; phenyl having up to five independent substituents selected from methyl, ethyl, methoxy, ethoxy; naphthyl having up to four independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-naphthyl-methyl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-(2-naphthyl)-ethyl-1-yl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; dialkylamine-NR5R6, wherein R5 and R6 are independently selected from C1-C4 alkyl groups;

[0038] R2 is selected from the straight chain C7-C. 10 Alkyl groups and straight-chain C7-C bonds with terminal C-C double bonds 10 alkenyl;

[0039] R3 is selected from H, Me, Et, phenyl, 2-naphthyl, 4-methoxyphenyl; and

[0040] R4 is selected from H and Me.

[0041] Compound (Ib) corresponds to compound (I) in which X is S (=O). Compound (Ib) includes sulfonates.

[0042] For example, a compound of formula (Ib) is a methanesulfonate ester in which R1 is methyl, or in which R1 is a toluene-based toluenesulfonate ester, and in which R2 to R4 are as defined above.

[0043] Compounds of formula (Ia) and (Ib) are subgroups of compounds of formula (I). Therefore, unless otherwise stated, the descriptions relating to compounds of formula (I) apply to compounds of formula (Ia) and (Ib).

[0044] Compounds of formula (I) may have a C-C double bond, which may have an E- or Z- configuration, or a mixture of E- and Z- configurations, unless otherwise specified.

[0045] Compounds of formula (I) have a stereocenter and exist in two enantiomers. Compounds of formula (I) can be enantiomerically pure, enriched, or racemic.

[0046] For example, C1-C 11 The alkyl group can be selected from methyl, ethyl, straight-chain or branched propyl (such as n-propyl, isopropyl), butyl (such as n-butyl, isobutyl, sec-butyl, tert-butyl, etc.), pentyl, hexyl, heptyl, octyl, nonyl, decyl and undecyl.

[0047] For example, straight-chain C7-C 10 The alkyl group can be selected from straight-chain heptyl, octyl, nonyl, and decyl.

[0048] For example, a straight-chain C7-C with a terminal C-C double bond.10 The alkenyl group can be selected from hept-6-en-1-yl, oct-7-en-1-yl, non-8-en-1-yl, and dec-9-en-1-yl.

[0049] For example, the use of compound (I) as a fragrance precursor capable of releasing fragrances with an aldehyde aroma profile is provided. Typically, the release of aromatic molecules is activated by external triggers such as hydrolysis, temperature changes, oxygen, light, and / or enzymatic action.

[0050] Some of the compounds in formula (I) are known from different backgrounds. For example, document WO2013060818A1 describes a method for preparing a group of compounds with related structures, which are suitable intermediates or precursors for the preparation of other chemical compounds. The term "intermediate or precursor" refers to a compound that is not used directly but is further transformed into different compounds through subsequent preparation steps. This document does not address fragrance precursors that can release fragrances with aldehyde aromas upon activation.

[0051] Typically, when freshly prepared, compounds of formula (I) are odorless or have a low odor and are capable of releasing fragrances, for example, those with an aldehyde aroma. However, in some embodiments of the invention, compounds of formula (I) may have their own odor.

[0052] By using the compound of formula (I), it is possible to provide an aldehyde fragrance over an extended period of time and to provide a sustained release of the aldehyde fragrance.

[0053] Aldehyde aromas provide an olfactory impression, which can often be described using other terms such as metallic, sharp, or penetrating (these are more of a physical impression or association). Terms also associated with aldehyde aromas include "oily aldehyde" or "aldehyde-green." The olfactory term "aldehyde aroma" is not strictly related to the chemical characteristics of the aldehyde in the molecular structure. Therefore, a typical aldehyde aroma serves as an olfactory reference, unrelated to the chemical characteristics of the aldehyde in the molecular structure.

[0054] For example, use of a compound of formula (I) as a fragrance precursor is provided, wherein the compound is selected from tetradec-1,13-dien-4-yl acetate, tetradec-1-en-4-yl acetate, tridec-1-en-4-yl acetate, tetradec-1-en-4-yl benzoate, tridec-1-en-4-yl benzoate, tetradec-1,13-dien-4-yl benzoate, 2-naphthoic acid tetradec-1,13-dien-4-yl ester, 2-naphthoic acid tridec-1-en-4-yl ester, 2-naphthoic acid tetradec-1-en-4-yl ester, 2-(naphtho-1-yl)acetic acid tetradec-1-en-4-yl ester, 2-(naphtho-1-yl)acetic acid tridec-1-en-4-yl ester, 2-(naphtho-1-yl)acetic acid tetra ... C1,13-diene-4-yl ester, 2-methylundecanoic acid tridec-1-en-4-yl ester, 2-methylundecanoic acid tetradec-1-en-4-yl ester, dimethylcarbamate tetradec-1-en-4-yl ester, methyltetradec-1-en-4-yl carbonate, pentadec-3-en-6-yl acetate, pentadec-3-en-6-yl benzoate, 3,4,5-trimethoxybenzoic acid tridec-1-en-4-yl ester, 3,4,5-trimethoxybenzoic acid tetradec-1-en-4-yl ester, undec-1-en-4-yl benzoate, dodecadec-1-en-4-yl benzoate, tetradec-1,13-diene-4-yl methanesulfonate, and 4-methylbenzenesulfonate tetradec-1,13-diene-4-yl ester.

[0055] According to one aspect of the invention, the use of a compound of formula (I) as a fragrance precursor is provided, wherein said compound is an ester, and wherein R1 is selected from straight-chain or branched C1-C1 compounds. 11 Alkyl; phenyl having up to five independent substituents selected from methyl, ethyl, methoxy, and ethoxy; naphthyl having up to four independent substituents selected from methyl, ethyl, methoxy, and ethoxy; 1-naphthyl-methyl having up to two independent substituents selected from methyl, ethyl, methoxy, and ethoxy; 1-(2-naphthyl)-ethyl-1-yl having up to two independent substituents selected from methyl, ethyl, methoxy, and ethoxy; and R2, R3, and R4 have the same meaning as defined above.

[0056] The compound of formula (I) above releases fragrance compounds when the precursor compound is exposed to ambient air for a long period of time (e.g., several days, such as 2-7 days or even longer).

[0057] Exposure of the precursor compound to ambient air means exposure to molecular oxygen, which may lead to the cleavage of compound (I) and the release of fragrance. The concentration of oxygen in the air is sufficient to cleave compound (I), allowing the cleavage products to be detected in ambient air, for example, through olfactory analysis of headspace samples.

[0058] Compounds of formula (I) are very stable when they are restricted or protected from exposure to ambient air, i.e., when stored in a pure form in a suitable container away from air and light, or when stored in suitable solvents such as ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butanediol, dipropylene glycol, isopropyl myristate, triethyl citrate, diethyl phthalate, triacetin, and / or diacetin, or when incorporated into consumer products such as detergents, shampoos, and fabric conditioners. Therefore, compounds of formula (I) can be used in a wide range of consumer products in which the prolonged and limited release of aromatic compounds is required.

[0059] Therefore, in another aspect of the invention, a method for releasing fragrance from a compound of formula (I) is provided, wherein the compound is exposed to an environmental trigger. For example, the environmental trigger is ambient air or other oxygen source.

[0060] In some embodiments, stabilizing compounds, such as α-tocopherol, EDTA, ascorbic acid, BHT, and Tinoguard TT, may be added to the compound of formula (I) at, for example, 0.01-1% by weight, to limit or prevent premature degradation of the compound of formula (I). In particular, stabilizing compounds may be used to enhance the stability of the pure compound of formula (I).

[0061] Compounds of formula (I) may be used alone or in combination with known flavoring molecules selected from a wide range of currently available natural or synthetic molecules, such as essential oils, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, macrocyclic and heterocyclic compounds, and / or in combination with one or more ingredients or excipients commonly used in fragrance compositions, such as carrier materials and other auxiliaries commonly used in the field. For example, these known flavoring molecules are described in "Perfume and Flavor Chemicals", S. Arctander, Ed., Vol. I & II, Allured Publishing Corporation, Carol Stream, USA, 2003, and include fragrance compounds and essential oils of natural or synthetic origin.

[0062] On the other hand, compounds of formula (I) can be used in combination with other fragrance precursors, with other compounds according to formula (I), or with precursors having different chemical structures. The combination of precursors allows for the release of fragrance aromas.

[0063] On the other hand, a flavoring composition is provided comprising at least one compound of formula (I). For example, the flavoring composition may also comprise one or more known flavoring molecules, and / or one or more ingredients or excipients that are conventionally used in combination with flavorings in a flavoring composition.

[0064] Depending on the effect the perfumer wants to achieve, the compound of formula (I) can be included in the fragrance composition in a wide range of amounts. For example, the compound can be used at 0.01-80% by weight, or 0.1-50% by weight, or 1-20% by weight. These values ​​are given by way of example only, and other amounts may also be applied.

[0065] As used in this article, “carrier material” refers to a material that is actually neutral from the perspective of flavor enhancers, that is, a material that does not significantly alter the sensory properties of flavor enhancers.

[0066] The term "auxiliary agent" refers to an ingredient that may be used in a fragrance composition for reasons not particularly related to the olfactory properties of the composition. For example, an auxiliary agent may be an ingredient that acts as an aid in processing one or more fragrance ingredients or a composition containing said ingredients, or it may improve the handling or storage of the fragrance ingredient or a composition containing said fragrance ingredient. It may also be an ingredient that provides additional benefits such as imparting color or texture. It may also be an ingredient that imparts lightfastness or chemical stability to one or more ingredients contained in the fragrance composition. A detailed description of the nature and type of auxiliary agents typically used in fragrance compositions containing auxiliary agents is not exhaustive, but it must be mentioned that such ingredients are well known to those skilled in the art.

[0067] As used herein, “fragrance composition” means any composition comprising a compound of formula (I) and a base material, such as a diluent conventionally used in combination with flavor enhancers, such as diethyl phthalate (DEP), dipropylene glycol (DPG), isopropyl myristate (IPM), pentyl-1,2-diol, triethyl citrate (TEC), and alcohols (e.g., ethanol). Optionally, the composition may contain an antioxidant auxiliary. The antioxidant may be selected from… TT (BASF) Q (BASF), tocopherol (including its isomers, CAS 59-02-9; 364-49-8; 18920-62-2; 121854-78-2), 2,6-bis(1,1-dimethylethyl)-4-methylphenol (BHT, CAS128-37-0) and related phenols, hydroquinone (CAS 121-31-9).

[0068] The following non-limiting list includes examples of known flavor enhancer molecules that can be combined with compounds of formula (I) in flavor compositions:

[0069] ● Essential oils and extracts, such as castoreum, costus root oil, oakmoss absolute oil, geranium oil, tree moss absolute oil, basil oil, fruit oils such as bergamot and mandarin oil, myrtle oil, palmarosa oil, patchouli oil, orange leaf oil, jasmine oil, rose oil, sandalwood oil, wormwood oil, lavender oil and / or ylang-ylang oil;

[0070] ● Alcohols, such as cinnamyl alcohol ((E)-3-phenylprop-2-en-1-ol); cis-3-hexenol ((Z)-hex-3-en-1-ol); citronellol (3,7-dimethyloct-6-en-1-ol); dihydromyrcenol (2,6-dimethyloct-7-en-2-ol); Ebanol TM ((E)-3-methyl-5-(2,2,3-trimethylcyclopentan-3-en-1-yl)pentan-4-en-2-ol); Eugenol (4-allyl-2-methoxyphenol); Ethyl linalool ((E)-3,7-dimethylnon-1,6-dien-3-ol); Farnesol ((2E,6Z)-3,7,11-trimethyldodec-2,6,10-trien-1-ol); Geraniol ((E)-3,7-dimethyloct-2,6-dien-1-ol); Super Muguet TM (E)-6-ethyl-3-methyloct-6-en-1-ol; linalool (3,7-dimethyloct-1,6-dien-3-ol); menthol (2-isopropyl-5-methylcyclohexanol); nerol (3,7-dimethyl-2,6-octadien-1-ol); phenylethanol (2-phenylethanol); Rhodinol TM (3,7-Dimethyloct-6-en-1-ol); Sandalore TM (3-Methyl-5-(2,2,3-trimethylcyclopentan-3-en-1-yl)pentan-2-ol); terpineol (2-(4-methylcyclohexane-3-en-1-yl)propan-2-ol); or Timberol TM (1-(2,2,6-trimethylcyclohexyl)hex-3-ol); 2,4,7-trimethyloct-2,6-dien-1-ol; and / or [1-methyl-2(5-methylhex-4-en-2-yl)cyclopropyl]-methanol;

[0071] ●Aldehydes and ketones, such as anisaldehyde (4-methoxybenzaldehyde); α-pentylcinnamaldehyde (2-benzylheptanal); Georgywood TM (1-(1,2,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphth-2-yl)acetone); hydroxycitronellol (7-hydroxy-3,7-dimethyloctanal); Iso E (1-(2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphth-2-yl)acetone); ((E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one); (3-oxo-2-pentylcyclopentane methyl acetate); Nympheal (3-(4-isobutyl-2-methylphenyl)propanal); Mahonial (5,9-dimethyl-9-hydroxy-decen-4-aldehyde); maltol; methyl cypressone; methyl ionone; verbenatenone; and / or vanillin;

[0072] ●Ethers and acetals, for example (3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b-octahydro-1H-benzo[e][1]benzofuran); geranyl methyl ether ((2E)-1-methoxy-3,7-dimethyloctyl-2,6-diene); rose ether (4-methyl-2-(2-methylprop-1-en-1-yl)tetrahydro-2H-pyran); and / or (2',2',3,7,7-pentamethylspiro[bicyclo[4.1.0]heptane-2,5'-[1,3]dioxane]);

[0073] ●Esters and lactones, such as benzyl acetate; cypress acetate (acetic acid (1S,6R,8aR)-1,4,4,6-tetramethyloctahydro-1H-5,8a-methylenechalcogenide-6-yl ester); γ-decyl lactone (6-pentyltetrahydro-2H-pyran-2-one); (2-[1-(3,3-dimethylcyclohexyl)ethoxy]-2-methylpropyl propionate); γ-undecanoic acid lactone (5-heptyloxacyclopentan-2-one); and / or vetiver acetate (4,8-dimethyl-2-prop-2-ylidene-3,3a,4,5,6,8a-hexahydro-1H-chamomilecyclo-6-yl) ester);

[0074] ● Macrocyclic compounds, such as asterolone ((Z)-oxetane-10-en-2-one); ethylene brassinolate (1,4-dioxetane-5,17-dione); and / or (16-oxacyclohexadecane-1-one); and

[0075] ● Heterocyclic compounds, such as isobutylquinoline (2-isobutylquinoline).

[0076] On the other hand, a consumer product is provided, comprising at least one compound of formula (I) and a consumer product base.

[0077] For example, the consumer products of the present invention are selected from detergents and cleaning agents, hygiene or care products, preferably in the fields of body and hair care, cosmetics and household products, and preferably selected from fragrance extracts, perfumes, eau de toilette, aftershave, cologne, pre-shaving products, spray cologne, scented refreshing wipes, acidic, alkaline or neutral detergents, fabric fresheners, ironing aids, liquid detergents, powder detergents, laundry pretreatment agents, fabric softeners, laundry sheets, laundry soaps, laundry tablets, bar soaps, disinfectants, surface disinfectants, air fresheners, aerosol sprays, waxes and polishes, body care products, hand creams and lotions, foot creams and lotions, hair removal creams and lotions, aftershave creams and lotions, tanning creams and lotions, hair care products (in liquid or solid form), dry shampoo, deodorants, antiperspirants, decorative cosmetics, candles, lamp oil, incense, insecticides, insect repellents and fuels.

[0078] Consumer products include, for example, those selected from fine fragrances, personal care products (body care products, hair care products, cosmetics), fabric care products, home care products, and air care products. As used herein, "consumer product base" refers to compositions used in consumer products to achieve specific functions such as cleaning, softening, and conditioning.

[0079] Personal care products that can contain compounds of formula (I) include, for example, all kinds of body care products. Of particular interest are hair care products, such as shampoos, conditioners, and hairsprays, and skin care products, such as lotions or creams. Furthermore, compounds of formula (I) can be added to soaps, bath gels and shower gels, and deodorants. Compounds of formula (I) can be added to cosmetics.

[0080] Additive (I) compound-based household care products include a variety of detergents, window cleaners, hard surface cleaners, general-purpose cleaners, and furniture polishes. Preferably, the product is a liquid, such as a fabric detergent or conditioning composition.

[0081] For example, compounds of formula (I) can serve as flavoring precursors in consumer products that further contain enzymes.

[0082] Compound (I) can be used in a wide range of fragranced consumer products, such as any area of ​​fine fragrances and functional fragrances, including perfumes, air care products, home products, laundry products, body care products, and cosmetics. The compound can be used in widely varying amounts, depending on the specific product and the nature and amount of other fragrance-enhancing ingredients. The proportion of Formula (I) is typically 0.0001 to 5% by weight of the product. In one embodiment, compound (I) can be used in fabric softeners in amounts of 0.001 to 0.3% by weight (e.g., 0.01 to 0.1%, including 0.05% by weight). In another embodiment, compound (I) can be used in fine fragrances in amounts of 0.001 to 30% by weight (e.g., up to about 10 or up to 20% by weight), more preferably 0.01 to 5% by weight, but also in consumer products such as shampoos, fabric softeners, or fabric detergents. However, these values ​​are given only by way of example, as experienced perfumers can also achieve the desired effect, or can produce novel fragrances with lower or higher concentrations.

[0083] In one embodiment, a consumer article is provided containing an acceptable amount of the compound of formula (I). For example, a flavored article may contain 0.000001 wt% to 90 wt% (including 0.00001 wt%; 0.0001 wt%, 0.001 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 5 wt%, 8 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 50 wt%, 60 wt%, 65 wt%) of the compound of formula (I), based on the total amount of the article.

[0084] Compounds of formula (I) can be used in consumer product bases simply by directly mixing the compounds of the present invention or fragrance compositions containing compounds of formula (I) with the consumer product base, or they can be encapsulated in an earlier step with encapsulating materials such as polymers, capsules, microcapsules and nanocapsules, liposomes, film-forming agents, absorbents such as carbon or zeolites, cyclic oligosaccharides and mixtures thereof, and then mixed with the consumer product base. The consumer product base may further contain encapsulating materials capable of releasing other aromatic compounds.

[0085] Therefore, the present invention further provides a method for manufacturing a consumer product, the method comprising incorporating the compound of formula (I) by directly mixing it into a consumer product base material using conventional techniques and methods, or by mixing a fragrance composition containing the compound of formula (I) and then mixing it with the consumer product base material. By adding an acceptable amount of the compound of the present invention as described above, the aroma and fragrance of the applied consumer product will be improved, imparted, enhanced, or altered.

[0086] Therefore, the present invention also provides, in another aspect, a method for imparting, enhancing, improving or altering the pleasurable properties of a fragrance composition or consumer product, the method comprising adding at least one compound of formula (I) to said composition or consumer product.

[0087] Some of the compounds of formula (I) are known in different applications; however, most of them are new.

[0088] Therefore, the present invention provides a compound of formula (I),

[0089]

[0090] in

[0091] X is selected from C and S (=O);

[0092] R1 is selected from straight chains or branched chains C1-C. 11 Alkyl; methoxy; ethoxy; phenyl having up to five independent substituents selected from methyl, ethyl, methoxy, ethoxy; naphthyl having up to four independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-naphthyl-methyl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-(2-naphthyl)-ethyl-1-yl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; dialkylamine-NR5R6, wherein R5 and R6 are independently selected from C1-C4 alkyl groups;

[0093] R2 is selected from the straight chain C7-C. 10 Alkyl groups and straight-chain C7-C bonds with terminal C-C double bonds 10 alkenyl;

[0094] R3 is selected from H, Me, Et, phenyl, 2-naphthyl, 4-methoxyphenyl; and

[0095] R4 is selected from H and Me.

[0096] The condition is that the compound is not tetradec-1-en-4-yl acetate, tridecdec-1-en-4-yl acetate, tetradecdec-1,13-dien-4-yl acetate, undecdec-1-en-4-yl benzoate, undecdec-1-en-4-yl neopentanoate, undecdec-1-en-4-yl acetate, methyl undecdec-1-en-4-yl carbonate, dodecdec-1,11-dien-4-yl acetate, or dodecdec-1-en-4-yl acetate.

[0097] For example, a compound of formula (Ia) is provided.

[0098]

[0099] in

[0100] R1 is selected from straight chains or branched chains C1-C. 11 Alkyl; methoxy; ethoxy; phenyl having up to five independent substituents selected from methyl, ethyl, methoxy, ethoxy; naphthyl having up to four independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-naphthyl-methyl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-(2-naphthyl)-ethyl-1-yl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; dialkylamine-NR5R6, wherein R5 and R6 are independently selected from C1-C4 alkyl groups;

[0101] R2 is selected from the straight chain C7-C. 10 Alkyl groups and straight-chain C7-C bonds with terminal C-C double bonds 10 alkenyl;

[0102] R3 is selected from H, Me, Et, phenyl, 2-naphthyl, 4-methoxyphenyl; and

[0103] R4 is selected from H and Me.

[0104] The condition is that the compound is not tetradec-1-en-4-yl acetate, tridecdec-1-en-4-yl acetate, tetradecdec-1,13-dien-4-yl acetate, undecdec-1-en-4-yl benzoate, undecdec-1-en-4-yl neopentanoate, undecdec-1-en-4-yl acetate, methyl undecdec-1-en-4-yl carbonate, dodecdec-1,11-dien-4-yl acetate, or dodecdec-1-en-4-yl acetate.

[0105] For example, a compound of formula (Ia) as defined above is provided, wherein R2 is selected from straight-chain C9-C. 10 Alkyl groups and straight-chain C7-C bonds with terminal C-C double bonds 10 Alkenyl group.

[0106] For example, compounds of formula (Ib) are provided.

[0107]

[0108] in

[0109] R1 is selected from straight chains or branched chains C1-C. 11Alkyl; methoxy; ethoxy; phenyl having up to five independent substituents selected from methyl, ethyl, methoxy, ethoxy; naphthyl having up to four independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-naphthyl-methyl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-(2-naphthyl)-ethyl-1-yl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; dialkylamine-NR5R6, wherein R5 and R6 are independently selected from C1-C4 alkyl groups;

[0110] R2 is selected from the straight chain C7-C. 10 Alkyl groups and straight-chain C7-C bonds with terminal C-C double bonds 10 alkenyl;

[0111] R3 is selected from H, Me, Et, phenyl, 2-naphthyl, 4-methoxyphenyl; and

[0112] R4 is selected from H and Me.

[0113] Compounds of formula (I) may have a C-C double bond, which may have an E- or Z- configuration, or a mixture of E- and Z- configurations, unless otherwise specified.

[0114] Compounds of formula (I) have a stereocenter and exist in two enantiomers. Compounds of formula (I) can be enantiomerically pure, enriched, or racemic.

[0115] For example, compounds of formula (I) are selected from tetradec-1-en-4-yl benzoate, tridec-1-en-4-yl benzoate, tetradec-1,13-dien-4-yl benzoate, tetradec-1,13-dien-4-yl 2-naphthoate, tridec-1-en-4-yl 2-naphthoate, tetradec-1-en-4-yl 2-naphthoate, tetradec-1-en-4-yl 2-(naphtho-1-yl)acetic acid, tridec-1-en-4-yl 2-(naphtho-1-yl)acetic acid, tetradec-1,13-dien-4-yl 2-methylundecanoate, and tridec-1-en-2-methylundecanoate. 4-yl ester, tetradec-1-en-4-yl ester of 2-methylundecanoate, tetradec-1-en-4-yl ester of dimethylcarbamate, methyl tetradec-1-en-4-yl ester of carbonate, (Z)-pentadecano-3-en-6-yl ester of acetate, (Z)-pentadecano-3-en-6-yl ester of benzoic acid, tridecane-1-en-4-yl ester of 3,4,5-trimethoxybenzoic acid, tetradecane-1-en-4-yl ester of 3,4,5-trimethoxybenzoic acid, dodecane-1-en-4-yl ester of benzoic acid, tetradecane-1,13-diene-4-yl ester of methanesulfonate, and tetradecane-1,13-diene-4-yl ester of 4-methylbenzenesulfonate.

[0116] Compounds of formula (I) can be prepared from alcohols by esterification with acyl chlorides or sulfonyl chlorides using methods known in the art.

[0117] Alternatively, compounds of formula (I) can be obtained by reacting an aldehyde with allyl magnesium chloride, followed by acylation of the resulting alcohol with an acyl anhydride or acyl chloride. For example, compounds of formula (I) can be prepared by a method in which allyl Grignard addition and ester formation are carried out in the same reaction vessel without intermediate separation or purification. A magnesium alkoxide is formed by Grignard addition, which further reacts with an acyl anhydride, acyl chloride, or sulfonyl chloride. In said one-pot reaction, no base is required to quench the Grignard reagent during acylation or between the two steps.

[0118] The invention will now be further described with reference to the following non-limiting embodiments. These embodiments are for illustrative purposes only, and it should be understood that changes and modifications can be made by those skilled in the art. Example

[0119] General

[0120] All reactions were performed under argon atmosphere using solvents and reagents from commercial suppliers without further purification. Solvents used for extraction and chromatography were industrial grade and used without further purification. Rapid chromatography was performed using silica gel (200-300 mesh) from Qingdao Haiyang Chemical Co., Ltd., and silica rapid columns from Santai Technologies (Changzhou) Co., Ltd. A mixture of heptane:MTBE was used as the eluent unless otherwise specified. NMR spectra were recorded using an AW 400MHz Bruker spectrometer. Chemical shifts 1 1H NMR spectra are reported in δ (ppm), with reference to the residual proton signal of the deuterated solvent; coupling constants are expressed in Hertz (Hz). 13 NMR spectra referenced the carbon signal of the deuterated solvent. The following abbreviations were used: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = double doublet, bs = broad singlet. GC / MS spectral data were obtained from an Agilent 6890N and MSD 5975, using an HP-5MS column (30m, 0.25mm, 0.25μm). High-resolution mass spectra were determined on a Thermo Fisher Scientific LTQ FT Ultra (ESI-MS) and a Waters Micromass GCT Premier (EI-MS).

[0121] Example 1: Tetradec-1,13-dien-4-yl acetate

[0122] Example 1a: Tetradecano-1,13-dien-4-ol

[0123] A solution of undecyl-10-enal (42.1 g, 50 mL, 250 mmol) in THF (tetrahydrofuran) (250 mL) was slowly treated with a solution of allyl magnesium chloride in THF (138 mL, 2 M, 276 mmol), and the resulting mixture was stirred overnight at 25 °C. The mixture was poured onto an ice-cold NH4Cl solution, extracted 2x with MTBE (methyl tert-butyl ether), washed with brine, dried over MgSO4, and evaporated. The crude product was purified by fractional distillation via a 5 cm Vigreux column to give tetradecyl-1,13-dien-4-ol (38.8 g, 68% yield, 92% purity) as a colorless liquid.

[0124] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 5.91-5.75 (m, 2H), 5.19-5.10 (m, 2H), 5.06-4.89 (m, 2H), 3.71-3.59 (m ,1H),2.36-2.27(m,1H),2.21-2.10(m,1H),2.09-2.00(m,2H),1.71(d,J=3.9Hz,1H),1.52-1.24(m,14H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 139.2, 134.9, 118.0, 114.1, 70.7, 41.9, 36.8, 33.8, 29.6, 29.5, 29.4, 29.1, 28.9, 25.7.

[0125] Example 1b: Tetradec-1,13-dien-4-yl acetate

[0126] A solution of tetradecyl-1,13-dien-4-ol (5.26 g, 25 mmol) in toluene (100 mL) was treated with pyridine (5.05 mL, 62.5 mmol) and DMAP (N,N-dimethylpyridine-4-amine) (92 mg, 0.75 mmol), followed by dropwise treatment with acetyl chloride (1.96 mL, 27.5 mmol) in toluene (25 mL) while cooled in a water bath. The resulting mixture was stirred at ambient temperature for 3 h, then poured onto ice-cold 2N HCl, extracted with MTBE, washed with brine, dried over MgSO4, and evaporated. The crude product was purified by Kugeljo distillation to give tetradecyl-1,13-dien-4-yl acetate (5.38 g, 20 mmol, 92% purity, 78% yield) as a colorless liquid.

[0127] 1H NMR (400MHz, CDCl3, 298K) δ (ppm) = 5.89-5.69 (m, 2H), 5.12-4.87 (m, 5H), 2. 38-2.21(m,2H),2.11-1.98(m,5H),1.62-1.49(m,2H),1.43-1.22(m,12H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 170.7, 139.1, 133.8, 117.5, 114.1, 73.3, 38.6, 33.8, 33.6, 29.4, 29.4, 29.4, 29.1, 28.9, 25.3, 21.2. MS(EI,70eV):211(2,[M +* -allyl]),192(0),135(3),95(5),81(5),67(5),55(7),43(100).

[0128] Odor description (1% EtOH solution on smelling paper, 24h): Aldehyde, oily odor, metallic odor, green odor, citrus odor.

[0129] Example 2: Tetradec-1-en-4-yl acetate

[0130] A solution of allyl magnesium chloride in THF (16.2 mL, 1.7 mol / L, 1.1 Eq, 27.5 mmol) was cooled to 0 °C and then slowly treated with a solution of undecylaldehyde (4.26 g, 5.16 mL, 1 Eq, 25.0 mmol) in THF (5 mL), and the resulting mixture was stirred at 0 °C for 2 h. The mixture was then slowly treated with acetic anhydride (3.06 g, 2.83 mL, 1.2 Eq, 30.0 mmol) at 0–15 °C and stirred at 25 °C for 1 h. The mixture was then poured onto 2N HCl (50 mL), extracted with MTBE (2 × 25 mL), and washed with saturated Na₂CO₃ solution (25 mL) and brine (25 mL). The organic layer was dried with MgSO4, filtered and concentrated to obtain a crude product, which was purified by Kugeljo distillation (oven at 175 °C / 0.097 mbar) to obtain tetradec-1-en-4-yl acetate (5.57 g, 21 mmol, 84% yield, 96% purity), a colorless liquid.

[0131] 1H NMR (400MHz, CDCl3, 298K) δ (ppm) = 5.76 (tdd, J = 7.2, 10.1, 17.1Hz, 1H), 5.15-5.03 (m, 2H), 4.92 (quin, J =6.2Hz,1H),2.37-2.26(m,2H),2.04(s,3H),1.60-1.50(m,2H),1.39-1.20(m,16H),0.93-0.86(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 170.8, 133.8, 117.5, 73.3, 38.6, 33.6, 31.9, 29.6, 29.6, 29.5, 29.4, 29.3, 25.3, 22.7, 21.2, 14.1.

[0132] MS(EI, 70eV): 213(1, [M +* -allyl]),194(1),153(2),111(5),97(12),83(7),67(5),55(7),43(100),41(12).

[0133] Odor description (1% EtOH solution on smelling paper, 24h): Aldehyde, oily odor, metallic odor, green odor, citrus odor, orange leaf odor.

[0134] Example 3: Tridecyl-1-en-4-yl acetate

[0135] According to the method described in Example 2, the compound was prepared using decanal (instead of undecaldehyde) to obtain tridecano-1-en-4-yl acetate (62% yield, 89% purity), which is a colorless liquid.

[0136] 1 H NMR (500MHz, CDCl3, 298K) δ (ppm) = 5.77 (tdd, J = 7.1, 10.1, 17.1Hz, 1H), 5.13-5.04 (m, 2H), 4.93 (quin, J = 6.3Hz,1H),2.38-2.27(m,2H),2.05(s,3H),1.59-1.52(m,2H),1.35-1.22(m,14H),0.90(t,J=7.0Hz,3H). 13 C NMR (126MHz, CDCl3, 298K) δ (ppm) = 170.8, 133.8, 117.5, 73.4, 38.7, 33.6, 31.9, 29.5, 29.5, 29.3, 25.3, 22.7, 21.2, 14.1.

[0137] MS(EI, 70eV): 199(1, [M +* -allyl]),180(1),157(1),139(3),97(5),83(9),67(4),55(6),43(100).

[0138] Odor description (1% EtOH solution on smelling paper, 24h): Aldehyde, oily odor, metallic odor, green odor, citrus odor.

[0139] Example 4: Tetradec-1-en-4-yl benzoate

[0140] According to the method described in Example 2, the compound was prepared using benzoyl chloride (instead of acetic anhydride) to obtain tetradec-1-en-4-yl benzoate (69% yield), which is a colorless liquid.

[0141] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 8.10-8.04 (m, 2H), 7.61-7.54 (m, 1H), 7.49-7.43 (m, 2H), 5.85 (tdd, J = 7.1, 10 .1,17.1Hz,1H),5.24-5.05(m,3H),2.52-2.43(m,2H),1.79-1.63(m,2H),1.47-1.20(m,16H),0.95-0.86(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 166.2, 133.7, 132.7, 130.8, 129.5, 128. 3,117.7,74.1,38.7,33.7,31.9,29.6,29.6,29.5,29.3,25.3,22.7,14.1. MS(EI,70eV):316(1,[M +* ]),287(1),194(2),123(2),105(100),77(14),41(6).

[0142] Odor description (1% EtOH solution on smelling paper, 24h): Aldehyde, oily odor, metallic odor, green odor, citrus odor, orange leaf odor.

[0143] Example 5: Tridecano-1-en-4-yl benzoate

[0144] According to the method described in Example 2, the compound was prepared using decanal (instead of undecaldehyde) and benzoyl chloride (instead of acetic anhydride) to obtain tridecano-1-en-4-yl benzoate (52% yield), which is a colorless liquid.

[0145] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 8.07 (dd, J = 1.3, 8.4Hz, 2H), 7.60-7.54 (m, 1H), 7.49-7.43 (m, 2H), 5.86 (tdd, J = 7.2, 10.1, 1 7.1Hz,1H),5.24-5.16(m,1H),5.16-5.05(m,2H),2.51-2.44(m,2H),1.76-1.64(m,2H),1.46-1.21(m,14H),0.93-0.86(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 166.2, 133.7, 132.7, 130.8, 129.5, 128.3, 117.7, 74.1, 38.7, 33.7, 31.9, 29.5, 29.5, 29.3, 25.3, 22.7, 14.1. MS(EI,70eV):302(1,[M +* ]),261(1),180(1),123(1),105(100),77(15),41(7).

[0146] Odor description (1% EtOH solution on smelling paper, 24h): Aldehyde, oily odor, green aroma, citrus aroma, orange leaf aroma.

[0147] Example 6: Tetradec-1,13-dien-4-yl benzoate

[0148] According to the method described in Example 1b, the compound was prepared using benzoyl chloride (instead of acetyl chloride) to obtain tetradec-1,13-diene-4-yl benzoate (77% yield), which is a colorless liquid.

[0149] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 8.10-8.04 (m, 2H), 7.61-7.54 (m, 1H), 7.50-7.41 (m, 2H), 5.92-5.76 ( m,2H),5.24-4.91(m,5H),2.50-2.44(m,2H),2.10-2.00(m,2H),1.83-1.62(m,2H),1.52-1.24(m,12H). 13C NMR (101MHz, CDCl3, 298K) δ (ppm) = 166.2, 139.2, 133.7, 132.7, 130.7, 129.5, 1 28.3,117.7,114.1,74.1,38.7,33.8,33.7,29.5,29.5,29.4,29.1,28.9,25.3. MS(EI,70eV):314(1,[M +* ]),273(1),192(1),123(2),105(100),77(13),41(7).

[0150] Odor description (1% EtOH solution on smelling paper, 24h): Aldehyde, oily odor, metallic odor, green odor, citrus odor.

[0151] Example 7: Tetradec-1,13-diene-4-yl ester of 2-naphthoic acid

[0152] According to the method described in Example 1b, the compound was prepared using 2-naphthoyl chloride (instead of acetyl chloride) to give tetradec-1,13-diene-4-yl benzoate (62% yield), which is a yellow liquid.

[0153] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 8.63 (d, J = 0.7Hz, 1H), 8.09 (dd, J = 1.7, 8.6Hz, 1H), 7.99 (d, J = 7.8Hz,1H),7.95-7.86(m,2H),7.65-7.53(m,2H),5.99-5.72(m,2H),5.34-5.21(m,1H),5.16(qd ,J=1.6,17.0Hz,1H),5.10(td,J=1.0,10.3Hz,1H),5.00(qd,J=1.8,17.1Hz,1H),4.94(tdd,J=1. 2,2.2,10.1Hz,1H),2.57-2.48(m,2H),2.09-1.98(m,2H),1.86-1.67(m,2H),1.52-1.22(m,12H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 166.4, 139.2, 135.5, 133.8, 132.5, 130.9, 129.3, 128.1, 12 8.1,128.0,127.7,126.6,125.3,117.8,114.1,74.2,38.8,33.8,33.7,29.4,29.1,28.9,25.4. MS(EI,70eV):364(1,[M+* ]),323(1),209(1),172(28),155(100),127(29),55(9),41(10).

[0154] Odor description (1% EtOH solution on scent paper, 24h): Aldehyde, green, metallic odor.

[0155] Example 8: 2-Naphthoic acid tridecano-1-en-4-yl ester

[0156] Example 8a: Tridecano-1-en-4-ol

[0157] The compound was prepared according to the method described in Example 1a, using decanal (instead of undec-10-enal) to obtain tridec-1-en-4-ol (95% yield), which is a pale yellow liquid.

[0158] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 5.85 (dddd, J = 6.4, 7.9, 9.6, 17.6Hz, 1H), 5.22-5.11 (m, 2 H),3.72-3.62(m,1H),2.33(tddd,J=1.3,4.2,6.5,13.9Hz,1H),2.22-2.09(m,1H),1.62(br d,J=11.5Hz,1H),1.54-1.23(m,16H),0.95-0.85(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 134.9, 118.0, 70.7, 41.9, 36.8, 31.9, 29.7, 29.6, 29.6, 29.3, 25.7, 22.7, 14.1.

[0159] Example 8b: 2-Naphthoic acid tridecano-1-en-4-yl ester

[0160] According to the method described in Example 1b, a compound was prepared using 2-naphthoyl chloride (instead of acetyl chloride) and tridecano-1-en-4-ol (instead of tetradecano-1,13-dien-4-ol) to obtain 2-naphthoic acid tridecano-1-en-4-yl ester (75% yield), which is a colorless liquid.

[0161] 1H NMR (400MHz, CDCl3, 298K) δ (ppm) = 8.62 (d, J = 0.7Hz, 1H), 8.09 (dd, J = 1.6, 8.7Hz, 1H), 8. 03-7.96(m,1H),7.91(d,J=8.6Hz,2H),7.65-7.52(m,2H),5.90(tdd,J=7.0,10.2,17.1Hz ,1H),5.27(qd,J=5.7,7.5Hz,1H),5.16(qd,J=1.6,17.0Hz,1H),5.10(tdd,J=1.0,2.0,1 0.0Hz,1H),2.57-2.48(m,2H),1.86-1.67(m,2H),1.52-1.20(m,14H),0.94-0.84(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 166.4, 135.5, 133.8, 132.5, 130.9, 129.3, 128.1, 128.1, 1 28.0,127.7,126.6,125.3,117.8,74.2,38.8,33.7,31.9,29.5,29.5,29.3,25.4,22.7,14.1. MS(EI,70eV):352(1,[M +* ]),337(1),311(1),172(26),155(100),127(31),55(5),41(9).

[0162] Odor description (1% EtOH solution on smelling paper, 24h): Aldehyde, green, metallic, orange leaf.

[0163] Example 9: Tetradec-1-en-4-yl ester of 2-naphthoic acid

[0164] Example 9a: Tetradec-1-en-4-ol

[0165] The compound was prepared according to the method described in Example 1a, using undecaldehyde (instead of undec-10-enal) to give tetradec-1-en-4-ol (96% yield), which is a colorless liquid.

[0166] 1H NMR (400MHz, CDCl3, 298K) δ (ppm) = 5.92-5.78 (m, 1H), 5.22-5.09 (m, 2H), 3.66 (br s,1H),2.32(tddd,J=1.3,4.2,6.6,13.9Hz,1H),2.21-2.10(m,1H),1.64(s,1H),1.54-1.22(m,18H),0.95-0.83(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 134.9, 118.0, 70.7, 41.9, 36.8, 31.9, 29.7, 29.6, 29.6, 29.3, 25.7, 25.6, 22.7, 14.1.

[0167] Example 9b: Tetradec-1-en-4-yl ester of 2-naphthoic acid

[0168] According to the method described in Example 1b, a compound was prepared using 2-naphthoyl chloride (instead of acetyl chloride) and tetradec-1-en-4-ol (instead of tetradec-1,13-dien-4-ol) to obtain tetradec-1-en-4-yl 2-naphthoic acid (66% yield), which is a colorless liquid.

[0169] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 8.62 (d, J = 0.7Hz, 1H), 8.09 (dd, J = 1.7, 8. 6Hz,1H),8.03-7.96(m,1H),7.91(d,J=8.6Hz,2H),7.66-7.53(m,2H),5.90(t dd,J=7.1,10.2,17.2Hz,1H),5.27(qd,J=5.9,7.4Hz,1H),5.20-5.06(m,2H), 2.57-2.49(m,2H),1.86-1.67(m,2H),1.52-1.19(m,16H),0.94-0.84(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 166.4, 135.5, 133.8, 132.5, 130.9, 129.3, 128.1, 128.1, 128.0, 127.7,126.6,125.3,117.8,77.2,74.2,38.8,33.7,31.9,29.6,29.6,29.5,29.3,25.4,22.7,14.1. MS(EI,70eV):366(1,[M +*]),325(1),194(2),172(27),155(100),127(29),55(5),41(9).

[0170] Odor description (1% EtOH solution on scent paper, 24h): green, metallic, aldehyde.

[0171] Example 10: 2-(naphthyl-1-yl)acetic acid tetradec-1-en-4-yl ester

[0172] According to the method described in Example 1b, the compound was prepared using 2-(naphthyl-1-yl)acetyl chloride (instead of acetyl chloride) and tetradec-1-en-4-ol (instead of tetradec-1,13-dien-4-ol) to give tetradec-1-en-4-yl 2-naphthocarboxylate (76% yield), which is a colorless liquid.

[0173] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 8.08-8.00 (m, 1H), 7.92-7.86 (m, 1H), 7.85-7.79 (m, 1H), 7.58-7.48 (m, 2H), 7.48-7.41 (m, 2H) ,5.73-5.60(m,1H),5.03-4.90(m,3H),4.08(s,2H),2.32-2.24(m,2H),1.56-1.46(m,2H),1.38-1.09(m,16H),0.97-0.89(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 171.3, 133.8, 133.6, 132.1, 130.9, 128.7, 128.0, 127.9, 126.2, 125 .7,125.4,124.0,117.5,73.9,39.6,38.6,33.5,31.9,29.6,29.5,29.5,29.4,29.4,25.1,22.7,14.1. MS(EI,70eV):380(15,[M +* ]),339(1),186(19),169(3),141(100),115(13).

[0174] Odor description (1% EtOH solution on smelling paper, 24h): Aldehyde, green, metallic, oily, citrus leaf, hot iron.

[0175] Example 11: 2-(naphthyl-1-yl)acetic acid tridec-1-en-4-yl ester

[0176] According to the method described in Example 1b, the compound was prepared using 2-(naphth-1-yl)acetyl chloride (instead of acetyl chloride) and tridecano-1-en-4-ol (instead of tetradecano-1,13-dien-4-ol) to give 2-(naphth-1-yl)acetic acid tridecano-1-en-4-yl ester (67% yield), which is a pale yellow liquid.

[0177] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 8.08-8.01 (m, 1H), 7.92-7.87 (m, 1H), 7.85-7.78 (m, 1H), 7.58-7.49 (m, 2H), 7.48-7.42 (m, 2H), 5 .74-5.61(m,1H),5.05-4.90(m,3H),4.08(s,2H),2.35-2.22(m,2H),1.57-1.45(m,2H),1.40-1.10(m,14H),0.93(t,J=7.0Hz,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 171.3, 133.8, 133.6, 132.1, 130.9, 128.7, 128.0, 127.9, 126.2, 125.7,125.4,124.0,117.6,73.9,39.6,38.6,33.6,31.9,29.5,29.5,29.4,29.3,25.1,22.7,14.2. MS(EI,70eV):366(7,[M +* ]),325(1),186(16),169(3),141(100),115(14),41(14).

[0178] Odor description (1% EtOH solution on smelling paper, 24h): green, citrus, aldehyde, metallic, oily, citrus leaf, hot iron.

[0179] Example 12: 2-(naphthyl-1-yl)acetic acid tetradec-1,13-dien-4-yl ester

[0180] According to the method described in Example 1b, the compound was prepared using 2-(naphth-1-yl)acetyl chloride (instead of acetyl chloride) to obtain 2-(naphth-1-yl)acetic acid tetradec-1,13-diene-4-yl ester (37% yield), which is a pale yellow liquid.

[0181] 1H NMR (400MHz, CDCl3, 298K) δ (ppm) = 8.07-8.01 (m, 1H), 7.92-7.86 (m, 1H), 7.8 1(dd,J=2.8,6.5Hz,1H),7.58-7.48(m,2H),7.48-7.42(m,2H),5.85(tdd,J= 6.6,10.3,17.1Hz,1H),5.73-5.60(m,1H),5.08-4.89(m,5H),4.08(s,2H),2 .32-2.23(m,2H),2.12-2.01(m,2H),1.56-1.44(m,2H),1.44-1.08(m,12H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 171.3, 139.2, 133.6, 132.1, 130.9, 128.7, 128.0, 127.9, 126. 2,125.7,125.4,124.0,117.6,114.1,73.9,39.6,38.6,33.8,33.5,29.4,29.3,29.1,28.9,25.1. MS(EI,70eV):378(7,[M +* ]),337(2),186(19),169(2),141(100),115(14),55(16).

[0182] Odor description (1% EtOH solution on smelling paper, 24h): Aldehyde, metallic, citrus leaf, hot iron, green.

[0183] Example 13: 2-Methylundecanoic acid tridec-1-en-4-yl ester

[0184] Example 13a: 2-Methylundecanoyl chloride

[0185] A mixture of 2-methylundecanoic acid (6.92 g, 1 Eq, 34.5 mmol) and DMF (N,N-dimethylformamide) (37.9 mg, 40.1 μL, 0.015 Eq, 518 μmol) was treated dropwise with thionyl chloride (14.4 g, 8.78 mL, 3.5 Eq, 121 mmol) at 10 °C with stirring at room temperature for 2 h. The resulting mixture was directly purified by Kugeljo distillation to give 2-methylundecanoic acid chloride (6.35 g, 33 mmol, 98% purity, 95% yield) as a colorless liquid.

[0186] 1H NMR (500MHz, CDCl3, 298K) δ (ppm) = 2.88 (sxt, J = 6.8Hz, 1H), 1.88-1.76 (m, 1H), 1.58-1.48 (m, 1H), 1.41-1.21 (m, 17H), 0.95-0.86 (m, 3H). 13 C NMR (126MHz, CDCl3, 298K) δ (ppm) = 177.8, 51.5, 33.4, 31.9, 29.5, 29.4, 29.4, 29.3, 26.7, 22.7, 17.0, 14.1.

[0187] Example 13b: 2-Methylundecanoic acid tridec-1-en-4-yl ester

[0188] According to the method described in Example 1b, the compound was prepared using 2-methylundecanoyl chloride (instead of acetyl chloride) and tridecano-1-en-4-ol (instead of tetradecano-1,13-dien-4-ol) to give 2-methylundecanoic acid tridecano-1-en-4-yl ester (68% yield), which is a colorless liquid (a mixture of 1:1 diastereomers).

[0189] 1 ¹H NMR (500MHz, CDCl₃, 298K, 1:1 diastereomer mixture) δ (ppm) = 5.82-5.70 (m, 1H), 5.11-5.04 (m, 2H), 4.97-4.90 (m, 1H), 2.46-2.37 (m, 1H), 2.37-2.26 (m, 2H), 1.71-1.61 (m, 1H), 1.60-1.51 (m, 2H), 1.44-1.36 (m, 1H), 1.36-1.21 (m, 28H), 1.17-1.12 (m, 3H), 0.93-0.86 (m, 6H). 13 C NMR (126MHz, CDCl3, 298K, 1:1 diastereomer mixture) δ (ppm) = 176.6, 176.5, 133.9, 117.4, 117.4, 72.8, 72.7, 40.0, 39.9, 38.8, 38.8, 33.9, 33.6, 31.9, 29.6, 29.5, 29.4, 27.3, 25.3, 25.3, 22.7, 17.3, 17.3, 14.1. MS (EI, 70eV): 380 (1, [M +*]),323(1),309(1),295(1),281(1),267(1),254(1),225(1),201(4),183(84),180(11),155(18),113(13),99(31),85(58),71(57),57(100),43(64).

[0190] Odor description (1% EtOH solution on scent paper, 24h): Aldehyde, metallic, balm, incense, citrus, green.

[0191] Example 14: Tetradec-1-en-4-yl ester of 2-methylundecanoate

[0192] According to the method described in Example 1b, the compound was prepared using 2-methylundecanoyl chloride (instead of acetyl chloride) and tetradec-1-en-4-ol (instead of tetradec-1,13-dien-4-ol) to give tetradec-1-en-4-yl 2-methylundecanoate (64% yield), which is a colorless liquid (a mixture of 1:1 diastereomers).

[0193] 1 ¹H NMR (500MHz, CDCl₃, 298K, 1:1 diastereomer mixture) δ (ppm) = 5.82-5.71 (m, 1H), 5.12-5.03 (m, 2H), 4.97-4.89 (m, 1H), 2.47-2.37 (m, 1H), 2.37-2.26 (m, 2H), 1.71-1.63 (m, 1H), 1.59-1.51 (m, 2H), 1.44-1.37 (m, 1H), 1.36-1.22 (m, 30H), 1.17-1.12 (m, 3H), 0.92-0.87 (m, 6H). 13 C NMR (126MHz, CDCl3, 298K, 1:1 diastereomer mixture) δ (ppm) = 176.6, 176.5, 133.9, 117.5, 117.5, 72.8, 72.7, 40.0, 39.9, 38.8, 38.8, 33.9, 33.6, 31.9, 29.6, 29.6, 29.6, 29.5, 29.4, 27.3, 25.3, 25.3, 22.7, 17.4, 17.3, 14.1. MS (EI, 70eV): 394 (1, [M +* ]),194(11),183(98),155(17),113(13),99(31),85(60),71(58),57(100),43(66).

[0194] Odor description (1% EtOH solution on scent paper, 24h): Aldehyde, metallic, balm, incense, citrus, green.

[0195] Example 15: Tetradec-1-en-4-yl dimethylcarbamate

[0196] A flask containing NaH (55% dispersion in mineral oil) (0.24 g, 5.5 mmol) and toluene (2.5 mL) was slowly treated with a solution of tetradec-1-en-4-ol (1.1 g, 5.0 mmol) in toluene (2.5 mL) at 25 °C, and the resulting mixture was heated under reflux for 1 h. The resulting mixture was cooled to 0 °C and slowly treated with a solution of dimethylcarbamoyl chloride (0.55 mL, 0.65 g, 6.0 mmol) in toluene (1.5 mL), and the mixture was stirred at 25 °C for 16 h. The mixture was then poured into water, extracted 2x with MTBE, washed with brine, dried over MgSO4, and purified by Kugeljo distillation to obtain tetradec-1-en-4-yl dimethylcarbamate (1.32 g, 90% purity, 84% yield) as a colorless liquid.

[0197] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 5.79 (tdd, J = 7.1, 10.1, 17.1Hz, 1H), 5.12-5.01 (m, 2H), 4.79 (quin, J = 6.1Hz, 1H), 2.91 (br s,6H),2.37-2.29(m,2H),1.61-1.51(m,2H),1.39-1.22(m,16H),0.93-0.86(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 156.5, 134.2, 117.2, 74.3, 38.9, 36.3 (br), 35.7 (br), 33.8, 31.9, 29.6, 29.3, 25.3, 22.7, 14.1. MS(EI,70eV):283(1,[M +* ]),242(1),194(3),90(16),72(100),41(13).

[0198] Odor description (1% EtOH solution on scent paper, 24h): powdery, aldehyde, oily, metallic, citrus, and green.

[0199] Example 16: Methyl tetradec-1-en-4-yl carbonate

[0200] According to the method described in Example 1b, a compound was prepared using methyl chloroformate (instead of acetyl chloride) and tetradec-1-en-4-ol (instead of tetradec-1,13-dien-4-ol) to obtain methyl tetradec-1-en-4-yl carbonate (87% yield), which is a colorless liquid.

[0201] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 5.79 (tdd, J = 7.1, 10.2, 17.2Hz, 1H), 5.15-5.06 (m, 2H), 4.80-4.7 0(m,1H),3.78(s,3H),2.41-2.34(m,2H),1.70-1.52(m,2H),1.42-1.21(m,16H),0.93-0.86(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 155.6, 133.3, 117.9, 77.9, 54.5, 38.5, 33.5, 31.9, 29.5, 29.3, 25.1, 22.7, 14.1. MS(EI,70eV):194(4,[M +* -HOC(O)OCH3]),153(4),111(28),97(100),83(85),77(14).

[0202] Odor description (1% EtOH solution on scent paper, 24h): Aldehyde, oily odor, metallic odor, green odor, marine odor.

[0203] Example 17: Acetic acid (Z)-pentadecano-3-en-6-yl ester

[0204] Example 17a: (Z)-Pentadeca-3-en-6-ol

[0205] Magnesium (495 mg, 1 Eq, 20.4 mmol) and 0.1 g of bromononane were added to a flask, and Grignard formation was initiated using a hot gun. A solution of 1-bromononane (4.22 g, 1 Eq, 20.4 mmol) in 20 mL of THF was added dropwise over 25 min. After addition, the reaction mixture was heated to 50 °C for 30 min until all magnesium shavings dissolved. The Grignard reagent was cooled to -20 °C and treated dropwise over 10 min with a solution of freshly distilled (Z)-hexane-3-enal (2.00 g, 1 Eq, 20.4 mmol) in 10 mL of THF. After addition, the cooling bath was removed, and the reaction mixture was stirred at ambient temperature for 1 h. The reaction mixture was poured into a saturated NH₄Cl⁻ solution and extracted 2x with MTBE, washed with water and brine until neutral, dried over MgSO₄, filtered, and concentrated. The obtained substance was purified by silica gel chromatography (eluting with a solution of MTBE in heptane), and then subjected to Courgel distillation to obtain (Z)-pentadecano-3-en-6-ol (1.4 g, 98% purity, 30% yield) as a colorless oil.

[0206] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 5.64-5.55 (m, 1H), 5.46-5.35 (m, 1H), 3.69-3.56 (m, 1H), 2.27-2.20 (m, 2H), 2.15-2.04 (m, 2H), 1.56 (br s,1H),1.53-1.41(m,2H),1.38-1.23(m,14H),0.99(t,J=7.5Hz,3H),0.94-0.87(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 135.1, 124.6, 71.5, 36.9, 35.2, 31.9, 29.7, 29.6, 29.6, 29.3, 25.8, 22.7, 20.7, 14.3, 14.1.

[0207] Example 17b: Acetic acid (Z)-pentadeca-3-en-6-yl ester

[0208] According to the method described in Example 1b, the compound was prepared using (Z)-pentadecano-3-en-6-ol (instead of tetradecano-1,13-dien-4-ol) to give (Z)-pentadecano-3-en-6-yl acetate (67% yield), which is a colorless liquid.

[0209] 1H NMR (400MHz, CDCl3, 298K) δ (ppm) = 5.55-5.46 (m, 1H), 5.38-5.27 (m, 1H), 4.89 (quin, J = 6.2Hz, 1H), 2.37-2.2 2(m,2H),2.11-2.01(m,4H),1.59-1.51(m,2H),1.37-1.23(m,14H),0.98(t,J=7.6Hz,3H),0.93-0.87(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 170.8, 134.3, 123.6, 74.0, 33.6, 31.9, 31.8, 29.5, 29.5, 29.3, 25.4, 22.7, 21.3, 20.6, 14.2, 14.1. MS(EI,70eV):208(7,[M +* -HOC(O)CH3]),199(1),95(10),82(24),43(100).

[0210] Odor description (1% EtOH solution on scent paper, 24h): Green, oily, watery, metallic, aldehyde, orange.

[0211] Example 18: Benzoic acid (Z)-pentadeca-3-en-6-yl ester

[0212] According to the method described in Example 1b, the compound was prepared using benzoyl chloride (instead of acetyl chloride) and (Z)-pentadecano-3-en-6-ol (instead of tetradecano-1,13-dien-4-ol) to obtain (Z)-pentadecano-3-en-6-yl benzoate (41% yield), which is a colorless liquid.

[0213] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 8.10-8.03 (m, 2H), 7.62-7.53 (m, 1H), 7.50-7.43 (m, 2H), 5.55-5.36 (m, 2H), 5.21-5.11 (m ,1H),2.55-2.36(m,2H),2.15-1.95(m,2H),1.79-1.62(m,2H),1.49-1.19(m,14H),0.96(t,J=7.6Hz,3H),0.92-0.86(m,3H).

[0214] 13C NMR (101MHz, CDCl3, 298K) δ (ppm) = 166.3, 134.4, 132.7, 130.8, 129.5, 129.5, 1 28.3,123.5,74.7,33.7,31.9,31.9,29.5,29.3,25.4,22.7,20.7,14.1,14.1. MS(EI,70eV):261(1),208(7),105(100),77(16).

[0215] Odor description (1% EtOH solution on scent paper, 24h): green, metallic, aldehyde, orange.

[0216] Example 19: 3,4,5-Trimethoxybenzoic acid tridec-1-en-4-yl ester

[0217] According to the method described in Example 1b, a compound was prepared using 3,4,5-trimethoxybenzoyl chloride (instead of acetyl chloride) and tridecano-1-en-4-ol (instead of tetradecano-1,13-dien-4-ol) to give 3,4,5-trimethoxybenzoic acid tridecano-1-en-4-yl ester (63% yield), which is a colorless liquid.

[0218] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 7.31 (s, 2H), 5.84 (tdd, J = 7.1, 10.2, 17.2Hz, 1H), 5.21-5.05 (m, 3H), 3.92(s,6H),3.91(s,3H),2.50-2.42(m,2H),1.81-1.61(m,2H),1.49-1.21(m,14H),0.92-0.84(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 165.8, 152.9, 142.1, 133.8, 125.8, 117.7, 106.8,74.3,60.9,56.2,38.7,33.7,31.9,29.5,29.5,29.3,25.3,22.7,14.1. MS(EI,70eV):392(11,[M +* ]),351(1),212(51),197(16),195(100),41(18).

[0219] Odor description (1% EtOH solution on smelling paper, 24h): Aldehyde, oily, green, metallic, vibrant, citrus, orange leaf.

[0220] Example 20: Tetradec-1-en-4-yl ester of 3,4,5-trimethoxybenzoic acid

[0221] According to the method described in Example 1b, a compound was prepared using 3,4,5-trimethoxybenzoyl chloride (instead of acetyl chloride) and tetradec-1-en-4-ol (instead of tetradec-1,13-dien-4-ol) to give tetradec-1-en-4-yl 3,4,5-trimethoxybenzoic acid (72% yield), which is a colorless liquid.

[0222] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 7.31 (s, 2H), 5.91-5.77 (m, 1H), 5.21-5.05 (m, 3H), 3.92 (s, 6H),3.92(s,3H),2.50-2.42(m,2H),1.79-1.61(m,2H),1.50-1.22(m,16H),0.92-0.84(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 165.9, 152.9, 142.1, 133.8, 125.8, 117.7, 106.8,74.3,60.9,56.2,38.7,33.7,31.9,29.6,29.5,29.3,25.4,22.7,14.1. MS(EI,70eV):406(11,[M +* ]),365(1),212(53),195(100).

[0223] Odor description (1% EtOH solution on smelling paper, 24h): green, aldehyde, oily, metallic, citrus, orange leaf.

[0224] Example 21: Undec-1-en-4-yl benzoate

[0225] Example 21a: Undec-1-en-4-ol

[0226] According to the method described in Example 1a, the compound was prepared using octanal (instead of undec-10-enal) to obtain undec-1-en-4-ol (98% yield), which is a pale yellow liquid.

[0227] 1H NMR (400MHz, CDCl3, 298K) δ (ppm) = 5.92-5.77 (m, 1H), 5.20-5.10 (m, 2H), 3.70-3.61 (m, 1H), 2.32 (tddd, J=1.3,4.1,6.6,13.9Hz,1H),2.21-2.09(m,1H),1.67(brs,1H),1.53-1.24(m,12H),0.95-0.85(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 134.9, 118.0, 70.7, 41.9, 36.8, 31.8, 29.6, 29.3, 25.7, 22.7, 14.1.

[0228] Example 21b: Undec-1-en-4-yl benzoate

[0229] According to the method described in Example 1b, a compound was prepared using benzoyl chloride (instead of acetyl chloride) and undec-1-en-4-ol (instead of tetradec-1,13-dien-4-ol) to obtain undec-1-en-4-yl benzoate (61% yield), which is a colorless liquid.

[0230] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 8.11-8.03 (m, 2H), 7.61-7.54 (m, 1H), 7.51-7.42 (m, 2H), 5.85 (tdd, J = 7.0, 10.1, 17.1H z,1H),5.24-5.16(m,1H),5.16-5.06(m,2H),2.52-2.42(m,2H),1.78-1.64(m,2H),1.50-1.20(m,10H),0.94-0.85(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 166.2, 133.7, 132.7, 130.7, 129.5, 128.3, 117.7, 74.1, 38.7, 33.7, 31.8, 29.5, 29.2, 25.3, 22.6, 14.1.

[0231] Odor description (1% EtOH solution on smelling paper, 24h): green, coriander, aldehyde, metallic, oily, birch leaf.

[0232] Example 22: Dodecano-1-en-4-yl benzoate

[0233] Example 22a: Dodecano-1-en-4-ol

[0234] According to the method described in Example 1a, the compound was prepared using nonanal (instead of undec-10-enal) to obtain dodec-1-en-4-ol (99% yield), which is a pale yellow liquid.

[0235] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 5.92-5.77 (m, 1H), 5.20-5.09 (m, 2H), 3.70-3.60 (m, 1H), 2.31 (tddd, J = 1 .3,4.2,6.6,13.9Hz,1H),2.20-2.09(m,1H),1.69(d,J=3.7Hz,1H),1.53-1.22(m,14H),0.94-0.85(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 134.9, 118.0, 70.7, 41.9, 36.8, 31.9, 29.7, 29.6, 29.3, 25.7, 22.7, 14.1.

[0236] Example 22b: Dodecano-1-en-4-yl benzoate

[0237] According to the method described in Example 1b, a compound was prepared using benzoyl chloride (instead of acetyl chloride) and dodecano-1-en-4-ol (instead of tetradecano-1,13-dien-4-ol) to obtain dodecano-1-en-4-yl benzoate (51% yield), which is a colorless liquid.

[0238] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 8.09-8.04 (m, 2H), 7.61-7.54 (m, 1H), 7.49-7.43 (m, 2H), 5.85 (tdd, J = 7.1, 10.2, 17.2H z,1H),5.24-5.16(m,1H),5.16-5.05(m,2H),2.53-2.43(m,2H),1.80-1.62(m,2H),1.48-1.20(m,12H),0.94-0.84(m,3H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 166.2, 133.7, 132.7, 129.5, 128.3, 117.7, 74.1, 38.7, 33.7, 31.8, 29.5, 29.5, 29.2, 25.3, 22.7, 14.1.

[0239] Odor description (1% EtOH solution on smelling paper, 24h): Aldehyde, metallic, oily, citrus, orange leaf.

[0240] Example 23: Application in liquid detergents

[0241] a) Sample preparation

[0242] 0.2% by weight of compound (I) was incorporated into an unscented liquid as a fragrance-enhancing detergent base by magnetic stirring at room temperature for 24 hours.

[0243] b) Washing tests and sensory evaluations

[0244] A 40°C machine wash cycle was performed using 55g of the liquid detergent sample prepared above and a cotton / elastomeric blend T-shirt with a neutral odor. A panel of 4-6 experts evaluated the odor intensity and quality of the wet and dry fabrics (day 1 and day 4). Odor intensity was recorded on a scale of 0 (odorless) to 5 (very strong).

[0245] Table 1

[0246]

[0247] As shown in Table 1, all tested materials exhibited very little odor during the wet stage, but released a fresh aldehyde fragrance over the following days, thus creating a strong odor impression on the dried fabric (score > 3), which even increased over time. The odor during the wet stage was always nonspecific and related to the blank odor of fabrics washed with unscented detergent.

[0248] Example 24: Tetradec-1,13-diene-4-yl methanesulfonate

[0249] A flask was filled with tetradecano-1,13-dien-4-ol (3.00 g, 14.3 mmol), triethylamine (1.73 g, 2.39 mL, 1.2 Eq, 17.1 mmol), and dichloromethane (DCM) (10 mL), and the mixture was cooled to 5 °C. The mixture was then treated dropwise at 5 °C with a solution of methanesulfonyl chloride (1.96 g, 1.32 mL, 1.2 Eq, 17.1 mmol) in DCM (4 mL). After the addition, the cooling bath was removed, and the yellow suspension was stirred at ambient temperature for 30 min. The reaction mixture was then poured into ice-cold 1 M HCl aqueous solution (100 mL) and extracted with MTBE (2 x 100 mL). The organic layer was washed with water and brine until neutral, dried over MgSO4, filtered, and concentrated. The crude substance was purified by silica gel chromatography to obtain tetradec-1,13-diene-4-yl mesylate (2.10 g, 51% yield), which was a colorless liquid.

[0250] 1 H NMR (400MHz, CDCl3, 298K) δ (ppm) = 5.91-5.73 (m, 2H), 5.22-5.14 (m, 2H), 5.05-4.92 (m, 2H), 4.75 (quin, J=6.1Hz,1H),3.01(s,3H),2.56-2.41(m,2H),2.12-2.00(m,2H),1.79-1.63(m,2H),1.50-1.24(m,12H). 13 C NMR (101MHz, CDCl3, 298K) δ (ppm) = 139.2, 132.6, 118.9, 114.1, 82.9, 39.0, 38.8, 34.2, 33.8, 29.4, 29.4, 29.3, 29.1, 28.9, 25.0.

[0251] MS (EI, 70 eV): 209(1, [M-CH3SO2] +* ),192(1),151(7),135(10),121(11),109(34),95(80),81(57),67(64),55(100),41(64).

[0252] Odor description (1% EtOH solution on smelling paper, 24h): Aldehyde, fresh, citrus, orange, hot iron, metallic, coriander.

[0253] Example 25: Tetradec-1,13-diene-4-yl 4-methylbenzenesulfonic acid

[0254] According to the method described in Example 24, p-toluenesulfonyl chloride (3.26 g, 1.2 Eq, 17.1 mmol) was used instead of methanesulfonyl chloride to obtain tetradec-1,13-diene-4-yl 4-methylbenzenesulfonic acid (2.20 g, 42% yield), which is a colorless liquid.

[0255] 1H NMR (400MHz, CDCl3, 298K) δ (ppm) = 7.85-7.78 (m, 2H), 7.35 (dd, J = 0.7, 8.6Hz, 2 H),5.83(tdd,J=6.6,10.3,17.1Hz,1H),5.73-5.59(m,1H),5.09-4.92(m,4H), 4.58(quin,J=6.1Hz,1H),2.46(s,3H),2.38(tddd,J=1.3,2.8,5.8,7.2Hz,2H) ,2.09-2.01(m,2H),1.64-1.53(m,2H),1.43-1.33(m,2H),1.33-1.12(m,12H). 13 CNMR (101MHz, CDCl3, 298K) δ (ppm) = 144.4, 139.2, 134.6, 132.3, 129.6, 127. 8,118.6,114.2,83.1,38.8,33.8,33.6,29.3,29.2,29.1,28.9,24.7,21.6.

[0256] Odor description (1% EtOH solution on smelling paper, 24h): Aldehyde, hot iron, citrus, metallic.

Claims

1. Use of compounds of formula (I) as fragrance precursors, in X is selected from C and S (=O); R1 is selected from straight chains or branched chains C1-C. 11 Alkyl; methoxy; ethoxy; phenyl having up to five independent substituents selected from methyl, ethyl, methoxy, ethoxy; naphthyl having up to four independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-naphthyl-methyl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-(2-naphthyl)-ethyl-1-yl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; dialkylamine-NR5R6, wherein R5 and R6 are independently selected from C1-C4 alkyl groups; R2 is selected from the straight chain C7-C. 10 Alkyl groups and straight-chain C7-C bonds with terminal C-C double bonds 10 alkenyl; R3 is selected from H, Me, Et, phenyl, 2-naphthyl, 4-methoxyphenyl; and R4 is selected from H and Me.

2. The use according to claim 1, wherein the compound of formula (I) is a compound of formula (Ia). As a precursor to fragrances, in R1 is selected from straight chains or branched chains C1-C. 11 Alkyl; methoxy; ethoxy; phenyl having up to five independent substituents selected from methyl, ethyl, methoxy, ethoxy; naphthyl having up to four independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-naphthyl-methyl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-(2-naphthyl)-ethyl-1-yl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; dialkylamine-NR5R6, wherein R5 and R6 are independently selected from C1-C4 alkyl groups; R2 is selected from the straight chain C7-C. 10 Alkyl groups and straight-chain C7-C bonds with terminal C-C double bonds 10 alkenyl; R3 is selected from H, Me, Et, phenyl, 2-naphthyl, 4-methoxyphenyl; and R4 is selected from H and Me.

3. The use according to claim 1, wherein the compound of formula (I) is a compound of formula (Ib). As a precursor to fragrances, in R1 is selected from straight chains or branched chains C1-C. 11 Alkyl; methoxy; ethoxy; phenyl having up to five independent substituents selected from methyl, ethyl, methoxy, ethoxy; naphthyl having up to four independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-naphthyl-methyl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-(2-naphthyl)-ethyl-1-yl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; dialkylamine-NR5R6, wherein R5 and R6 are independently selected from C1-C4 alkyl groups; R2 is selected from the straight chain C7-C. 10 Alkyl groups and straight-chain C7-C bonds with terminal C-C double bonds 10 alkenyl; R3 is selected from H, Me, Et, phenyl, 2-naphthyl, 4-methoxyphenyl; and R4 is selected from H and Me.

4. The use according to claim 1, wherein the compound of formula (I) is selected from tetradec-1,13-dien-4-yl acetate, tetradec-1-en-4-yl acetate, tridecdec-1-en-4-yl acetate, tetradec-1-en-4-yl benzoate, tridecdec-1-en-4-yl benzoate, tetradec-1,13-dien-4-yl benzoate, 2-naphthoic acid tetradec-1,13-dien-4-yl ester, 2-naphthoic acid tridecdec-1-en-4-yl ester, 2-naphthoic acid tetradec-1-en-4-yl ester, 2-(naphtho-1-yl)acetic acid tetradec-1-en-4-yl ester, 2-(naphtho-1-yl)acetic acid tridecdec-1-en-4-yl ester, 2-(naphtho-1-yl)acetic acid tetra ...1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1-1- 1,13-diene-4-yl ester, 2-methylundecanoic acid tridec-1-en-4-yl ester, 2-methylundecanoic acid tetradec-1-en-4-yl ester, dimethylcarbamate tetradec-1-en-4-yl ester, methyltetradec-1-en-4-yl carbonate, pentadec-3-en-6-yl acetate, pentadec-3-en-6-yl benzoate, 3,4,5-trimethoxybenzoic acid tridec-1-en-4-yl ester, 3,4,5-trimethoxybenzoic acid tetradec-1-en-4-yl ester, undec-1-en-4-yl benzoate, dodecadec-1-en-4-yl benzoate, tetradec-1,13-diene-4-yl methanesulfonate, and 4-methylbenzenesulfonate tetradec-1,13-diene-4-yl ester.

5. Compound of formula (I) in X is selected from C and S (=O); R1 is selected from straight chains or branched chains C1-C. 11 Alkyl; methoxy; ethoxy; phenyl having up to five independent substituents selected from methyl, ethyl, methoxy, ethoxy; naphthyl having up to four independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-naphthyl-methyl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-(2-naphthyl)-ethyl-1-yl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; dialkylamine-NR5R6, wherein R5 and R6 are independently selected from C1-C4 alkyl groups; R2 is selected from the straight chain C7-C. 10 Alkyl groups and straight-chain C7-C bonds with terminal C-C double bonds 10 alkenyl; R3 is selected from H, Me, Et, phenyl, 2-naphthyl, 4-methoxyphenyl; and R4 is selected from H and Me. The condition is that the compound is not tetradec-1-en-4-yl acetate, tridecdec-1-en-4-yl acetate, tetradecdec-1,13-dien-4-yl acetate, undecdec-1-en-4-yl benzoate, undecdec-1-en-4-yl neopentanoate, undecdec-1-en-4-yl acetate, methyl undecdec-1-en-4-yl carbonate, dodecdec-1,11-dien-4-yl acetate, or dodecdec-1-en-4-yl acetate.

6. The compound according to claim 5, wherein the compound of formula (I) is a compound of formula (Ia). in R1 is selected from straight chains or branched chains C1-C. 11 Alkyl; methoxy; ethoxy; phenyl having up to five independent substituents selected from methyl, ethyl, methoxy, ethoxy; naphthyl having up to four independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-naphthyl-methyl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-(2-naphthyl)-ethyl-1-yl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; dialkylamine-NR5R6, wherein R5 and R6 are independently selected from C1-C4 alkyl groups; R2 is selected from the straight chain C7-C. 10 Alkyl groups and straight-chain C7-C bonds with terminal C-C double bonds 10 alkenyl; R3 is selected from H, Me, Et, phenyl, 2-naphthyl, 4-methoxyphenyl; and R4 is selected from H and Me.

7. The compound according to claim 5, wherein the compound of formula (I) is a compound of formula (Ib). in R1 is selected from straight chains or branched chains C1-C. 11 Alkyl; methoxy; ethoxy; phenyl having up to five independent substituents selected from methyl, ethyl, methoxy, ethoxy; naphthyl having up to four independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-naphthyl-methyl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; 1-(2-naphthyl)-ethyl-1-yl having up to two independent substituents selected from methyl, ethyl, methoxy, ethoxy; dialkylamine-NR5R6, wherein R5 and R6 are independently selected from C1-C4 alkyl groups; R2 is selected from the straight chain C7-C. 10 Alkyl groups and straight-chain C7-C bonds with terminal C-C double bonds 10 alkenyl; R3 is selected from H, Me, Et, phenyl, 2-naphthyl, 4-methoxyphenyl; and R4 is selected from H and Me.

8. The compound according to claim 5, wherein the compound of formula (I) is selected from tetradec-1-en-4-yl benzoate, tridec-1-en-4-yl benzoate, tetradec-1,13-dien-4-yl benzoate, tetradec-1,13-dien-4-yl 2-naphthoate, tridec-1-en-4-yl 2-naphthoate, tetradec-1-en-4-yl 2-naphthoate, tetradec-1-en-4-yl 2-(naphtho-1-yl)acetic acid, tridec-1-en-4-yl 2-(naphtho-1-yl)acetic acid, tetradec-1,13-dien-4-yl 2-methyl The following are listed: tridecano-1-en-4-yl ester of undecanoate, tetradecano-1-en-4-yl ester of 2-methylundecanoate, tetradecano-1-en-4-yl ester of dimethylcarbamate, methyl tetradecano-1-en-4-yl ester of carbonate, pentadecano-3-en-6-yl ester of acetate, pentadecano-3-en-6-yl ester of benzoate, tridecano-1-en-4-yl ester of 3,4,5-trimethoxybenzoate, tetradecano-1-en-4-yl ester of 3,4,5-trimethoxybenzoate, dodecadecano-1-en-4-yl ester of benzoate, tetradecano-1,13-diene-4-yl ester of methanesulfonate, and tetradecano-1,13-diene-4-yl ester of 4-methylbenzenesulfonate.

9. A flavoring composition comprising at least one compound of formula (I) as defined in claim 1.

10. A consumer product comprising at least one compound of formula (I) as defined in claim 1 and a consumer product base.

11. The consumer product of claim 10, wherein the consumer product is selected from home care products and personal care products.

12. The consumer product of claim 11, wherein the consumer product is selected from liquid detergents and shampoos.

13. A method for releasing a fragrance from a compound of formula (I) as defined in claim 1, wherein the compound is exposed to environmental triggering factors.

14. A method for preparing the compound of formula (I) as defined in claim 1, comprising the following steps: a) React the aldehyde with allyl magnesium chloride, and b) React the resulting product with an acyl anhydride, acyl chloride, or sulfonyl chloride. Steps a) and b) are carried out as a one-pot reaction.

15. A method of imparting, enhancing, improving or altering a pleasant property to a fragrance composition or consumer product, the method comprising adding at least one compound of formula (I) as defined in claim 1 to said composition or consumer product.

16. The method of claim 15, wherein the at least one compound is exposed to environmental triggers.

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