Fragrances and compositions containing fragrances

Abstract

The present invention relates to a new class of perfuming 3-(2-methylenealkoxy)alkanenitrile derivatives that are useful as fragrance or flavoring materials, particularly in imparting dry, woody, dusty, earthy, and / or patchouli notes, as well as optional coriander, aldehydic, citrus, mandarin, pear, cinnamon, and / or petal floral-like notes to perfume, aroma, or deodorizing / masking compositions.

Description

[Technical Field]

[0001] The present invention relates to a new class of perfuming 3-(2-methylenealkoxy)alkanenitrile derivatives useful as fragrance or flavoring materials, particularly in imparting dry, woody, dusty, earthy, and / or patchouli notes, as well as optional coriander, aldehydic, citrus, mandarin, pear, cinnamon, and / or petal floral notes to perfume, aroma, or deodorizing / masking compositions. The present invention also relates to fragrance, flavor, and / or deodorizing / masking compositions comprising the new class of perfuming 3-(2-methylenealkoxy)alkanenitrile derivatives. The present invention further relates to the odorants that can be used in the novel fragrance, flavor, and / or deodorizing / masking compositions of the present invention. The present invention also relates to methods for producing the odorants / compounds and corresponding fragrance, flavor, and / or deodorizing / masking compositions comprising the odorants / compounds. [Background technology]

[0002] Nitriles represent an important class of organic compounds used in the perfume and fragrance industries. They are more chemically stable than the corresponding aldehydes. In fact, an important feature of the nitrile group is its robustness in acidic or basic media. There are saturated and unsaturated aliphatic nitriles with both linear and branched carbon skeletons, alicyclic nitriles and aromatic nitriles, as well as nitriles containing a combination of aromatic and aliphatic substituents (Non-Patent Document 1).

[0003] For example, Patent Document 1 discloses Parmanyl (3-(hexenyloxy)-propane-nitrile) and several other compounds consisting of the following, in which 3-(hexenyloxy)-propanenitrile of the general formula R3-O-CHR1-CHR2-CN (wherein R3 is an unbranched hexenyl residue, and R1 and R2 are selected from the group consisting of H and CH3) is claimed. The nine compounds disclosed in Table 1 of Patent Document 1 exhibit mainly green and fruity odor notes. Patent Document 2 claims 3-(2-methylbut-1-oxy)-2-methylpropionitrile and 3-(3-methylbut-1-oxy)-2-methylpropionitrile compounds useful as fragrance materials having a jasmine-type odor with a lactone note. Patent Document 3 discloses compounds of the general formula R-(CH2) m -A-(CH2) n discloses ether nitriles of the formula -O-(CH)-CN, where R is H, (CH)CH, or CHC(=CH), A is a C-C bond or C(CH)=CH, m is 1-8, and n is 1-5, provided that the total number of C's in the general formula is 7-15. The compounds disclosed include 3-((3-methylbut-3-en-1-yl)oxy)propanenitrile, n-hexyloxypropionitrile, n-octyloxypropionitrile, and geranyloxypropiontrile. Patent Document 3 states that the compounds claimed therein have an odor of floral, aromatic, and fruity character. Patent Document 4 discloses 3-(10-undecenyloxy)-propanenitrile, which was reported to have a weak fruity odor (reminiscent of pineapple).

[0004] In the ongoing search for novel fragrance molecules with unique odor profiles that can satisfy the demands of the fragrance industry, the present inventors have been interested in novel organic compounds with various sensory effects on compositions. During this search, the present inventors designed 3-(2-methylenealkoxy)alkanenitrile derivatives. Surprisingly, the present inventors have found that compounds of general formula (I), which can be derived from 2-methylene-aldehydes, have unique and diverse odor profiles, such as dry notes, woody notes, dusty notes, earthy notes, and / or patchouli notes. The present inventors have also found that the claimed compounds can be synthesized in a stepwise manner that is advantageous compared to the prior art. Finally, the present inventors have found that the claimed compounds, and the claimed perfume, aroma, and / or deodorizing / masking compositions containing the compounds, exhibit excellent properties, particularly stability properties. It is instructive to note that compounds such as Parmanil have different odor characteristics compared to the compounds represented in formula (I). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent No. 5,294,602 [Patent Document 2] International Publication No. 9413626 Brochure [Patent Document 3] German Patent No. 2601825 [Patent Document 4] German Patent No. 2639182 [Non-patent literature]

[0006] [Non-Patent Document 1] Mark Erman, Perfumer & Flavorist, Vol. 27, pp. 30-34, 2002 Summary of the Invention [Means for solving the problem]

[0007] The present invention relates to a compound of formula (I) [ka] (wherein R1 is a hydrogen atom or a methyl group; R2 is a hydrogen atom or an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms; R3 is either an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms; and R4 is a hydrogen atom or a methyl group, or an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms, with the proviso that If R3 is a methyl group, R2 is hydrogen, and R4 is hydrogen, then R1 cannot be hydrogen or a methyl group, and The present invention discloses novel fragrance, flavor, and / or deodorizing / masking compositions comprising substituted 3-(2-methylenealkoxy)alkanenitrile derivatives selected from the following compounds: (wherein R3 is a methyl group, R2 is hydrogen, and R4 is a methyl group, then R1 cannot be hydrogen).

[0008] In embodiments according to the invention, R2 may advantageously be a linear and / or branched alkyl / alkenyl, for example R2 is an alkyl / alkenyl group having up to 5 carbon atoms. In embodiments according to the invention, R3 may advantageously be a linear and / or branched alkyl / alkenyl.

[0009] In an embodiment according to the invention, R3 is methyl, ethyl, n-propyl, i-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or 9-octenyl.

[0010] In an embodiment according to the invention, R2 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or 9-octenyl.

[0011] In an embodiment according to the invention, R4 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or 9-octenyl. In an embodiment according to the invention, R4 is a hydrogen atom or a methyl group, or an alkyl group having up to 4 carbon atoms, for example a hydrogen atom or a methyl group.

[0012] In another embodiment, the compounds of formula (I) of the present invention can be chiral. For example, these compounds can be used as stereoisomeric (enantiomer or diastereomer) mixtures. In another embodiment, the compounds of formula (I) of the present invention can be chiral. For example, these compounds can be used as stereoisomeric (enantiomer or diastereomer) mixtures, more specifically as mixtures of enantiomers, and racemic mixtures and / or non-racemic mixtures of isomers can also be advantageously used. In another embodiment, the compounds of formula (I) can be advantageously used in pure form. DETAILED DESCRIPTION OF THE INVENTION

[0013] Detailed Description The term "flavoring agent" used to characterize the compounds according to the present invention means that they evoke a preferably pleasant odor sensation in humans. Thus, flavoring agents are conventionally used to flavor industrial and sanitary products, cleaning agents, cleaners, personal hygiene products, cosmetics, etc. For the purposes of this invention and the appended claims, the term "flavoring agent" includes "aromatics," a term commonly used to refer to substances that impart odor and / or flavor to food.

[0014] The alkeneoxynitrile compounds of formula (I) can be used alone, as mixtures thereof, or in combination with a base material.

[0015] As used herein, "base material" includes any known fragrance / flavoring material selected from a wide range of natural products, such as essential oils, extracts, resinoids, or isolates, as well as currently available synthetic materials, such as hydrocarbons, alcohols, aldehydes and ketones, ethers and acetals, esters and lactones, nitriles, oximes, or heterocyclic compounds, and / or mixtures with one or more ingredients or excipients / adjuvants customarily used in combination with flavoring agents in fragrance and / or flavor compositions, such as solvents / diluents, stabilizers, carrier materials, and other adjuvants commonly used in the art.

[0016] The alkeneoxynitrile compounds of formula (I) can be used in a wide range of fragrance applications, including all areas of fine perfumery and functional perfumery, such as perfumes, air care products, household products, laundry products, body care products, and cosmetics. The compounds can be used in a wide variety of amounts, depending on the particular application and the nature and amount of other perfume ingredients.

[0017] According to a preferred embodiment of the present invention, the fragrance, flavor and / or deodorizing / masking composition according to the invention comprises at least one alkeneoxynitrile compound of formula (I) as defined above in an amount of at least 0.00001% by weight, such as at least 0.0001% by weight, for example at least 0.001% by weight, preferably at least 0.01% by weight, more advantageously at least 0.1% by weight and in particular at least 1% by weight, in each case relative to the total composition; in one embodiment the alkeneoxynitrile compound of formula (I) as defined above is present in the composition in an amount of less than 99.9% by weight, such as less than 95% by weight, for example less than 50% by weight, preferably less than 25% by weight, for example less than 15% by weight, less than 10% by weight or even less than 5% by weight, in each case relative to the total composition.

[0018] According to a particularly preferred embodiment of the present invention, in addition to the compound of formula (I) according to the present invention, the fragrance, flavor and / or deodorizing / masking composition according to the present invention comprises an additional odorant, for example in an amount of 0.1% to 99.9% by weight, preferably 5% to 90% by weight, in particular 15% to 70% by weight, based on the total fragrance and / or flavor composition.

[0019] The compounds of formula (I) above may be used in a consumer product base simply by directly mixing at least one compound of formula (I) or a fragrance composition comprising a compound of formula (I) above with the consumer product base, or they may be entrapped at an earlier stage by an entrapment material, for example, a polymer, a capsule, a microcapsule, and / or a nanocapsule, a liposome, a film-forming agent, an absorbent such as activated carbon or zeolite, a cyclic oligosaccharide, a cyclic glycouril, and mixtures of two or more thereof, or they may be chemically bound to a substrate adapted to release the fragrance molecules upon application of an external stimulus such as light, an enzyme, air, water, etc., and then mixed with the consumer product base.

[0020] Thus, the present invention may be useful in existing methods for producing fragrance, flavor, and / or deodorizing / masking compositions, which involve incorporating a compound of formula (I) as a fragrance, flavor, and / or deodorizing / masking composition either by directly incorporating the compound into the consumer product base, or by mixing a fragrance, flavor, and / or deodorizing / masking composition comprising said compound of formula (I), which can then be mixed with the consumer product base using conventional techniques and methods. By adding an olfactory-acceptable amount of at least one compound of formula (I) of the present invention as described above, the odor notes of the consumer product base may be improved, enhanced, and / or modified.

[0021] The present invention relates to a compound of formula (I) [ka] (wherein R1 is a hydrogen atom or a methyl group; R2 is a hydrogen atom or an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms; R3 is an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms; and R4 is a hydrogen atom or a methyl group, or an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms, with the proviso that If R3 is a methyl group, R2 is hydrogen, and R4 is hydrogen, then R1 cannot be hydrogen or a methyl group, and The present invention discloses novel fragrance, flavor, and / or deodorizing / masking compositions comprising substituted 3-(2-methylenealkoxy)alkanenitrile derivatives selected from the following compounds: (wherein R3 is a methyl group, R2 is hydrogen, and R4 is a methyl group, then R1 cannot be hydrogen).

[0022] In an embodiment according to the present invention, the fragrance, flavor and / or deodorizing / masking composition comprises one or more compounds of formula (I) selected from the following compounds:

[0023] 1) 3-(3-methyl-2-methylenebutoxy)propanenitrile 2) 3-((5-methyl-4-methylenehexan-3-yl)oxy)butanenitrile 3) 3-(2-methylenebutoxy)propanenitrile 4) 3-(2-methylenebutoxy)butanenitrile 5) 3-((3-methylenepentan-2-yl)oxy)propanenitrile 6) 3-((3-methylenepentan-2-yl)oxy)butanenitrile 7) 3-((4-methylenehexan-3-yl)oxy)propanenitrile 8) 3-((4-methylenehexan-3-yl)oxy)butanenitrile 9) 3-((2-methylenepentyl)oxy)propanenitrile 10) 3-((3-methylenehexan-2-yl)oxy)propanenitrile 11) 3-((3-methylenehexan-2-yl)oxy)butanenitrile 12) 3-((4-methyleneheptan-3-yl)oxy)propanenitrile 13) 3-((2-methylenehexyl)oxy)propanenitrile 14) 3-((2-methylenehexyl)oxy)butanenitrile 15) 3-((4-methyleneoctan-3-yl)oxy)propanenitrile 16) 3-((4-methyleneoctan-3-yl)oxy)butanenitrile 17) 3-((2-methyleneheptyl)oxy)propanenitrile 18) 3-((2-methyleneheptyl)oxy)butanenitrile 19) 3-((3-methyleneoctan-2-yl)oxy)propanenitrile 20) 3-((3-methyleneoctan-2-yl)oxy)butanenitrile 21) 3-((4-methylenenonan-3-yl)oxy)propanenitrile 22) 3-((4-methylenenonan-3-yl)oxy)butanenitrile 23) 3-((2-methyleneoctyl)oxy)butanenitrile 24) 3-((3-methylenenonan-2-yl)oxy)propanenitrile 25) 3-((4-methylenedecan-3-yl)oxy)propanenitrile 26) 3-((4-methylenedecan-3-yl)oxy)butanenitrile 27) 3-((2-methylenenonyl)oxy)propanenitrile 28) 3-((3-methylenedecan-2-yl)oxy)propanenitrile 29) 3-((3-methylenedecan-2-yl)oxy)butanenitrile 30) 3-((2-methylenedec-9-en-1-yl)oxy)propanenitrile 31) 3-((2-methylenedec-9-en-1-yl)oxy)butanenitrile 32) 3-((2-methyl-5-methylenenonan-4-yl)oxy)propanenitrile 33) 3-((2-methyl-5-methylenenonan-4-yl)oxy)butanenitrile 34) 3-((6-methylenedecan-5-yl)oxy)propanenitrile 35) 3-((6-methylenedecan-5-yl)oxy)butanenitrile 36) 2-(((2-methylenehexyl)oxy)methyl)hexanenitrile 37) 2-(((2-methylenehexyl)oxy)methyl)pentanenitrile 38) 3-Methyl-2-(((2-methylenehexyl)oxy)methyl)butanenitrile 39) 2-((3-methyl-2-methylenebutoxy)methyl)pentanenitrile 40) 3-((5-methylenenon-1-en-4-yl)oxy)propanenitrile 41) 3-((5-methylenenon-1-en-4-yl)oxy)butanenitrile 42) 2-(((2-methylenehexyl)oxy)methyl)butanenitrile.

[0024] In one embodiment, the present invention also provides novel compounds of formula (I) useful in fragrance, flavor, and / or deodorizing / masking compositions. [ka] (wherein R1 is a hydrogen atom or a methyl group; R2 is a hydrogen atom or an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms; R3 is an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms; and R4 is a hydrogen atom or a methyl group, or an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms, with the proviso that If R3 is a methyl group, R2 is hydrogen, and R4 is hydrogen, then R1 cannot be hydrogen or a methyl group, and The present invention claims compounds (preferably novel odorant compounds of formula (I)) of the formula (I) wherein R3 is a methyl group, R2 is hydrogen, and R4 is a methyl group, and R1 cannot be hydrogen.

[0025] In an embodiment according to the invention, R2 may advantageously be linear and / or branched alkyl / alkenyl. In an embodiment according to the invention, R3 may advantageously be linear and / or branched alkyl / alkenyl. In an embodiment according to the invention, R4 may advantageously be linear and / or branched alkyl / alkenyl.

[0026] In an embodiment according to the invention, R3 is methyl, ethyl, n-propyl, i-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or 9-octenyl. In an embodiment according to the invention, R2 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or 9-octenyl.

[0027] In an embodiment according to the invention, R4 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or 9-octenyl. In an embodiment according to the invention, R4 is a hydrogen atom or a methyl group, or an alkyl group having up to 4 carbon atoms, for example a hydrogen atom or a methyl group.

[0028] In one embodiment, the present invention also claims the use of the novel compounds of formula (I) above in fragrance, flavor, and / or deodorizing / masking compositions to impart dry, woody, dusty, earthy, and / or patchouli notes, as well as optional coriander, aldehydic, citrus, mandarin, pear, cinnamon, and / or petal-floral-like notes to said compositions.

[0029] In an embodiment according to the present invention, the fragrance, flavor, and / or deodorizing / masking composition comprises a compound of formula (I) selected from any of the compounds set out above and / or mixtures of two or more of the above compounds.

[0030] Through sensory evaluation studies, the present applicants have also found that the compound represented by formula (I) can further exhibit aldehydic, coriander-like, citrus, mandarin, pear, and cinnamon-like profiles that enhance the freshness of citrus compositions. Furthermore, the compound represented by formula (I) exhibits woody, earthy, and dusty notes. Furthermore, the compound represented by formula (I) can also impart floral, vegetative, and green notes.

[0031] The present applicants have surprisingly found that compounds of general formula (I) enhance the effects of various types of fragrance compositions, as will be described in detail below.

[0032] It was very interesting to note that depending on the type of composition, different effects could be observed, such as a strong woody, a strong citrus or a strong rose effect.

[0033] In embodiments of the present invention, the claimed fragrance, flavor, and / or deodorizing / masking compositions are advantageously used as perfume compositions. Perfume compositions according to the present invention generally include perfumes, colognes, eau de toilettes, and / or eau de parfums. In embodiments of the present invention, the claimed fragrance, flavor, and / or deodorizing / masking compositions are advantageously used in cosmetic formulations, personal care products, cleansing products, fabric softeners, and / or air fresheners, etc. Furthermore, it is within the scope of embodiments of the present invention that the novel fragrance, flavor, and / or deodorizing / masking composition(s) and / or compound(s) of Formula (I) described herein may be incorporated into building materials, wall and floor coverings, vehicle parts, etc.

[0034] Generally, in addition to the novel odorants and / or fragrance, flavor, and / or deodorizing / masking compositions described herein, suitable fragrance, flavor, or deodorizing compositions may advantageously include conventional ingredients such as, for example, solvents, carriers, stabilizers, emulsifiers, humectants, dispersants, diluents, thickeners, thinning agents, other flavoring agents, and / or adjuvants.

[0035] By combining the compounds of formula (I) with many known natural or synthetic fragrance, flavor, and / or deodorizing / masking materials, the range of natural ingredients can be incorporated, not only readily volatile but also semi-volatile and less volatile ingredients, and the range of synthetic ingredients can be incorporated, as described in Steffen Arctander, Perfume and Flavor Chemicals, Vols. 1 and 2, Montclair, NJ, 1969; Steffen Arctander, Perfume and Flavor Materials of Natural Origin, Elizabeth, NJ, 1960; or Horst Surburg and Johannes Panten, Common Fragrance and Flavor Materials. Representatives of substances from many classes can be incorporated, as will become apparent from the following non-limiting compilations: (1) "Chemical Materials", Wiley-VCH, Weinheim, 2016; (2) "Chemical Materials", Wiley-VCH, Weinheim, 2016; (3) "Chemical Materials", Wiley-VCH, Weinheim, 2016; (4) "Chemical Materials", Wiley-VCH, Weinheim, 2016; (5

[0036] Natural products such as: Ajowan oil, Amyris oil, Armoise oil, Artemisia oil, Basil oil, Beeswax absolute, Bergamot oil, Birch tar oil, Black pepper oil, Black pepper oleoresin, Camphor oil, Cananga oil, Caraway oil, Cardamom oil, Carrot seed oil, Castoreum absolute, Cedar leaf oil, Cedarwood oil, Celery seed oil, Chamomile oil, Cinnamon bark oil, Cinnamon leaf oil, Cistus absolute, Cistus oil, Citronella oil, Citronella terpenes, Clary sage oil, Rectified clove oil, White cognac oil, Coriander Dah seed oil, cumin seed oil, cypress oil, davana oil, dill seed oil, elemi oil, elemi resinoids, eucalyptus oil, fir needle oil, galbanum oil, geranium oil, Indian ginger oil, grapefruit oil, guaiac wood oil, guruyun balsam, jasmine absolute, jatamansi oil, juniper berry oil, juniper leaf oil, kachur oil, labdanum absolute, labdanum resinoids, lavender oil, lemon oil, lemon oil terpenes, lemongrass oil, lime oil, litsea cubeba oil, litsea cubeba terpenes, choya loban choya resinoid, mandarin oil, Mentha arVenis oil, bergamot mint oil, mimosa absolute, myrrh resinoid, nagarmot oil, nutmeg oil, oakmoss absolute, oakmoss resinoid, olibanum oil, olibanum resinoid, orange oil, origanum oil, palmarosa oil, patchouli oil, peppermint oil, Peru balsam resinoid, petitgrain oil, pine needle oil, pink pepper oil, rose absolute, rose oil, rosemary oil, sandalwood oil, seaweed absolute, spearmint oil, sugandha kokila oil, sugandha mantri oil, taget oil, tolu balsam resinoid, tuberose absolute, turmeric oil, turpentine, valerian oil, vetiver oil, vetiver terpenes.

[0037] Synthetic raw materials, such as: esters, such as: aldehyde C16, allyl amyl glycolate, allyl caproate, allyl cyclohexylpropionate, allyl heptanoate, allyl phenoxyacetate, isoamyl acetate, amyl benzoate, amyl butyrate, amyl caproate, amyl cinnamate, amyl isovalerate, amyl phenylacetate, amyl propionate, isoamyl salicylate, amyris acetate, anisyl acetate, benzyl acetate, benzyl benzoate, benzyl butyrate, benzyl cinnamate, benzyl formate, benzyl isobutyrate, benzyl isoeugenol, benzyl propionate Benzyl salicylate, benzyl tiglate, butyl acetate, butyl butyrate, butyl butyryl lactate, caryophyllene acetate, cedryl acetate, cinnamyl acetate, cinnamyl butyrate, cis-3-hexenyl acetate, cis-3-hexenyl benzoate, cis-3-hexenyl caproate, cis-3-hexenyl formate, cis-3-hexenyl isobutyrate, cis-3-hexenyl-2-methyl butyrate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, cis-3-hexenyl tiglate, citronellyl acetate, citronellyl butyrate, citronellyl formate, citronellyl isobutyrate Ronellyl, citronellyl propionate, citronellyl tiglate, cyclabute, cyclogalbanate, cyclohexylethyl acetate, decyl acetate, dibutyl phthalate, diethyl malonate, diethyl phthalate, dihydromyrcenyl acetate, octanyl dimethyl acetate, dimethylphenylethylcarbinyl acetate, dioctyl adipate, dioctyl phthalate, dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, linalyl acetate, ethyl 2-methylbutyrate, ethyl 3-phenylpropionate, ethyl acetate, ethyl acetoacetate, ethyl benzoate, Ethyl butyrate, ethyl caprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethyl heptanoate, ethyl hexyl acetate, ethyl isobutyrate, ethyl laurate, ethyl pelargonate, ethyl phenoxyacetate, ethyl phenylacetate, ethyl phenylglycidate, ethyl propionate, ethyl saffronate, ethyl salicylate, ethyl valerate, eugenyl acetate, evernyl, fenchyl acetate, Floramat, Frescolate ML, fractone, fruitate, geranyl acetate, geranyl butyrate, geranyl formate, geranyl propionate, geranyl tiglate,Dibescon, Guaiol Acetate, Hedionate, Hedione, Helbetolide, Herbanate, Hexyl Acetate, Hexyl Benzoate, n-Hexyl Butyrate, Hexyl Caproate, Hexyl Isobutyrate, Hexyl Propionate, Hexyl Salicylate, Isobornyl Acetate, Isobutyl Acetate, Phenylisobutyl Acetate, Isobutyl Salicylate, Isoeugenyl Acetate, Isononyl Acetate, Isopene Thiate, isopropyl 2-methylbutyrate, isopropyl myristate, jasmonyl, rifarom, linalyl acetate, mahagonate, manzanate, menthyl acetate, menthyl acetate, methyl benzoate, 2-methylbutyl acetate, methyl chamomile, methyl cinnamate, methyl cyclogeranate, methyl heptine carbonate, methyl laurate, methyl octyne carbonate, methyl phenylacetate, methyl salicylate, methyl 2-methylbutyrate, neophorin , Nopyr acetate, Octenyl acetate, Octyl acetate, Octyl isobutyrate, Paracresyl acetate, Paracresyl isobutyrate, Paracresyl phenylacetate, Pear ester, Peranat, Phenoxyethyl isobutyrate, Phenylethyl acetate, Phenylethyl butyrate, Phenylethyl formate, Phenylethyl isobutyrate, Phenylethyl phenylacetate, Phenylethyl propionate, Phenylethyl salicylate, Phenylethyl tiglate, Phenylpropyl isobutyrate, Prenyl acetate, Lomandride, Sagecete, Styrallyl acetate, Styrallyl propionate, Tangerinol, Terpinyl acetate, Thesalone, Trans-2-hexenyl acetate, Tropicate, Verdox, Verdyl acetate, Verdyl propionate, Vertenex, Veticol acetate, Vetiveryl acetate, Yasmolys.

[0038] Lactones, such as: Ambrettolide, AroVaN, Celeriax, Delta Decalactone, Gamma Decalactone, Delta Dodecalactone, Gamma Dodecalactone, Ethylene Brassilelate, Exaltolide, Gamma Heptalactone, Delta Hexalactone, Gamma Hexalactone, Methyl Laitone, Methyl Octalactone, Delta Nonalactone, Gamma Nonalactone, Octahydrocoumarin, Delta Octalactone, Gamma Octalactone, Rootylone, SilVanone Supra, Deltaun Decalactone, Gamma Undecalactone, Gamma Valerolactone, 10-Oxahexadecanolide (OHD Musk), Coumarin, Habanolide, Jasmolactone.

[0039] Aldehydes, for example: Acetaldehyde, Adoxal, Aldehyde C10, Aldehyde C11 iso, Aldehyde C11 moa, Undecylenic aldehyde C11, Undecyl aldehyde C11, Lauryl aldehyde C12, Aldehyde C12 MNA, Anisaldehyde, Amyl Cinnamaldehyde, Benzaldehyde, Bourgeonal, Campholenaldehyde, Cantonal, Cetnal, Cinnamic Aldehyde, Cis-4-Decenal, Cis-6-Nonenal, Citral, Citronellal, Citronellyloxyacetaldehyde, Cocal, Cuminaldehyde, Curgix, Cyclal C, Cyclamen Aldehyde, Cyclomyral, Cycloberthal, Decenal 9, Dupical, Empethal, Ethyl Vanillin, Floralozone, Florhydral, Geraldehyde, Helional, Heliotropin, Heptanal, Hexanal, Hexyl Cinnamaldehyde, Hibernal Neo , hydratropaldehyde, hydroxycitronellal, intrelevenaldehyde, isobutan, isocyclocitral, isovaleraldehyde, lilial, limonenal, maceal, mefranal, melonal, methyl cinnamaldehyde, trans,cis-2,6-nonadienal, nonanal, octanal, oncidal, para-tolylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, precyclemone B, safranal, salicylic aldehyde, centenal, syringaldehyde, trans-4-decenal, trans-2-dodecenal, trans-2-hexenal, trans-2-nonenal, triphenal, vanillin, veratraldehyde, verniciflua.

[0040] Ketones, such as: acetanisole, acetoin, acetophenone, aldron, allylionone, benzophenone, benzylacetone, chalone, camphor, d-carvone, l-carvone, cashmeran, cedryl methyl ketone, sepionate, Claritone, cosmon, chrysolide, cyclotene, damascenone, damascone alpha, damascone beta, damascone delta, damascone gamma, diacetyl, dihydro beta ionone, dihydro isojasmonate, dimethyl octenone, dynascone, ethyl amyl ketone, ethyl maltol, fenchone, filbertone, geranyl acetone, globanone, heptyl cyclopentanone, alpha ionone, beta ionone, pure ionone, iris wood, alpha ionone, iso E super, isofenchone, iso Jasmone T, Isolone K, Isomenthone, Isophorone, cis-Jasmone, Kambernoir, Cephalis, Coavon, Lavendinal, Maltol, Menthone, Methylacetophenone, Methyl Amyl Ketone, Methylheptenone, Methylhexyl Ketone, Gamma Methyl Ionone, Methyl Naphthyl Ketone Beta, Methyl Nonyl Ketone, Muscenone, Muscone, Nectaryl, Orinox, OTBC Ketone, Para-Tertbutylcyclohexanone, Patchwood, Phantolide, Pharaon, Piperitone, Plicatone, Raspberry Ketone, Raspberry Ketone Methyl Ether, Safralein, Pure Spirogalbanone, Tonalide, Trimofix O, Veloutone, Vetikon.

[0041] Alcohols such as: Oxoalcohol C13, Ambercore, Ambermax, Ambrinol, Amylvinylcarbinol, Anise Alcohol, Bacdanol, Benzyl Alcohol, Butanol, Cedrol Crystal, Cinnamal Alcohol, Citronellol, Kolanol, Decanol, Dimethylbenzylcarbinol, Dimethyloctanol, Dimethylphenylethylcarbinol, Dimetol, Fenchol, Hexanol, Isoborneol, Isobornylcyclohexanol, Javanol, Keflorol, Kohinool, Lauryl Alcohol, Lilyflore, Linalool Oxide, Mayol, Menthol, Norlimbanol, Octanol, Oscilol, Para-tertbutyl Cyclohexanol, phenoxanol, phenoxyethanol, phenylethyl alcohol, phenylpropyl alcohol, propylene glycol, rosafen, rose glycol, styrallyl alcohol, tricyclodecane dimethanol, tetrahydrolinalool, tetrahydromyrcenol, timberol, undecavertol, cis-3-hexenol, levocitronellol, cyclofloranol, dihydrolinalool, dihydromyrcenol, dimyrcetol, evaporol, geraniol, isopulegol, linalool, nerol, nerolidol, trans,cis-2,6-nonadienol, polysanthol, rosalva, sandalwood, sandalwood, terpinen-4-ol, terpineol, trans-2-hexenol.

[0042] Phenols, for example: butylhydroxyanisole, dihydroeugenol, dimethylhydroquinone, dimethylresorcinol, pure eugenol, guaiacol, isoeugenol, metacresol, methyldianthrix, paracresol, propenylguaethol, thymol, ultravanil.

[0043] Ethers, such as: Ambroxan, Anethole, Anthracene, Benzyl Isoamyl Ether, Benzyl Isopropyl Ether, Benzyl Isovalerate, Boyalis, Cedrumbar, Cetalox, Decyl Methyl Ether, Dibenzyl Ether, Dihydrorose Oxide, Diphenyl Oxide, Dremox, Estragole, Ethyl Linalool, Eucalyptol, Galaxolide, Gyrane, HerbaVert, Lime Oxide, Madrox, Methyl Isoeugenol, Naphthyl Isobutyl Ether Beta, Nerol Oxide, Neroline Bromeliad, Paracresyl Butyl Ether, Paracresyl Methyl Ether, Petiole, Phenylethyl Methyl Ether, Rhubarb, Rose Oxide, Rosilan, Trisamber, Vetylbois K, Yara Yara.

[0044] Acetals, for example: Acetal CD, Acetal R, Amberketal, Boisambrene Forte, Citrathal, 1,1-Diethoxyethane, Emeraldine, Freshopal, Halboxane, Indoflor, Jacinthaflor, Magnolan, Spirambrene, Viridine, Ellinthal, Glycolieral, Caranal, Methyl Pamplemousse.

[0045] Hydrocarbons, for example: bisabolene, camphene, delta 3 carene, caryophyllene, cedrene, para-cymene, dipentene, diphenylmethane, isolongifolene, d-limonene, longifolene, myrcene, naphthalene, ocimene, alpha-pinene, beta-pinene, styrene, gamma-terpinene, terpinolene, 1,3,5-undecatriene, verdracin.

[0046] Sulfur compounds, for example: Corpus cassis, dibutyl sulfide, dimethyl sulfide, ExoVert, grapefruit thiol, oxane, Ribes mercaptan, sulfurol, thiocineol.

[0047] Nitriles, for example: cinnamyl nitrile, citronellyl nitrile, citronitrile, clonal, cumin nitrile, hexylcyclopentanone, iris nitrile, lemonyl, pionyl, tridecyl nitrile, agrumen nitrile, n-decyl nitrile.

[0048] Oximes, for example: buccoxim, labienoxim, stemone.

[0049] Nitrogen heterocycles, for example: 2-acetylpyrazine, 2-acetylpyridine, sec-butylquinoline, Corpus Racine, 2-ethyl-3,5(or 6)-dimethylpyrazine, furfurylpyrrole, indole, isobutylquinoline, 2-isobutyl-3(or 6)-methoxypyrazine, isopropylquinoline, maritime, p-methylquinoline, skatole, 2,3,5-trimethylpyrazine.

[0050] Nitro compounds, for example: musk ketone.

[0051] Schiff bases, for example: Aurantiol, Helianthral, ​​Ligantral, Verdantiol.

[0052] Other materials include: Acetanilide, Gardamide, Paradisamide, Dimethyl Anthranilate, Methyl Anthranilate, n-Butyric Acid, Capric Acid, Caproic Acid, Caprylic Acid, Phenylacetic Acid, Caryophyllene Oxide, Cedroxide, Tovacarol.

[0053] Thus, the compounds of formula (I) can be used not only to prepare compositions, but also to prepare a wide range of known odorants / fragrances, flavors, and / or deodorizing / masking materials, as is evident from the above-mentioned compilations. In preparing such compositions, the known fragrances, flavors, and / or deodorizing / masking materials mentioned above can be used according to methods known to perfumers, for example, according to W. A. ​​Poucher, Perfumes, Cosmetics and Soaps 2, 7th Edition, Chapman and Hall, London, 1974.

[0054] In an embodiment of the invention, the claimed fragrance, flavor and / or deodorizing / masking compositions comprise, in addition to the compound(s) of formula (I), at least one ester and / or one alcohol, preferably a mixture of at least an ester and an alcohol, said ester and / or alcohol preferably being selected from the list defined herein above. In an embodiment of the invention, the claimed perfuming compositions are characterized in that the total content of the compound(s) of formula (I) together with the ester(s) and / or alcohol(s) is greater than 25% by weight, preferably greater than 50% by weight, for example greater than 75% by weight or even greater than 90% by weight.

[0055] preparation According to an embodiment of the present invention, a compound of formula (I) [ka] wherein R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom or an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms, R3 is an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms, and R4 is a hydrogen atom or a methyl group, or an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms, and is advantageously a compound of formula (II) [ka] (wherein R2 is a hydrogen atom or either an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms, and R3 is either an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms) can be prepared by reacting the corresponding allylic alcohol substituted at the 2- and / or 1-position of formula (II) with acrylonitrile, crotonitrile ((E)-but-2-enenitrile), or a substituted 2-methylenenitrile.

[0056] In embodiments according to the invention, R2 may advantageously be linear and / or branched alkyl / alkenyl. In embodiments according to the invention, R3 may advantageously be linear and / or branched alkyl / alkenyl.

[0057] The above reaction between the compound of formula (II) and acrylonitrile or crotonitrile to prepare our compound of formula (I) is preferably carried out in the presence of a base (e.g., KOH) and a phase transfer catalyst selected from tetra-n-butylammonium bromide or 18-crown-6 ((CHO)), in a water-methylene chloride mixture. The reaction is advantageously carried out at ambient temperature, preferably between 15°C and 30°C, for example 25°C.

[0058] The resulting 3-(2-methylenealkoxy)alkanenitrile derivative of formula (I) is then purified, preferably by distillation.

[0059] In an embodiment according to the invention, the alcohol defined in formula (II) is advantageously of formula (III) [ka] It can be synthesized from acrolein substituted at the 2-position with (wherein R3 is either an alkyl group (linear and / or branched alkyl) having up to 9 carbon atoms or an alkenyl group (linear and / or branched alkyl) containing up to 9 carbon atoms) by, for example, reduction with sodium borohydride or lithium aluminum hydride, or by nucleophilic addition of an organometallic reagent, for example an appropriate alkyl magnesium halide, RMgX, e.g., MeMgCl.

[0060] In an embodiment of the present invention, the acrolein of formula (III) is advantageously acrolein of formula (IV) [ka] (wherein R3 is either an alkyl group (linear and / or branched alkyl) having up to 9 carbon atoms or an alkenyl group (linear and / or branched alkyl) having up to 9 carbon atoms) can be synthesized via the reaction of an aldehyde with formaldehyde (or a formaldehyde source).

[0061] For example, this reaction can be advantageously carried out by using formaldehyde (e.g., 37% aqueous formaldehyde solution) or a formaldehyde source (e.g., paraformaldehyde) and a combination of boric acid and a secondary amine, for example, a combination of boric acid and a secondary amine such as diethanolamine. In an embodiment of the present invention, the aldehyde and formaldehyde can also be reacted using an acid-base combination of 4-methoxybenzoic acid and di-n-butylamine. The reaction of the aldehyde and formaldehyde results in the formation of acrolein substituted at the 2-position of formula (III) as defined above.

[0062] In an embodiment according to the present invention, the substituted 2-methylenenitrile (V) [ka] can be prepared in two steps by first converting a substituted α-methylene aldehyde (III) to the corresponding oxime (VI), followed by dehydration.

[0063] Preparation of nitrile (V) in two steps Oximes (VI) made from 2-substituted acroleins (III): The 2-substituted nitriles were purchased from commercial sources (R = H) and otherwise prepared as shown in the following scheme.

[0064] [ka]

[0065] In an embodiment according to the present invention, a compound of formula (VI) [ka] The oxime defined in the formula (III) (wherein R3 is either an alkyl group (linear and / or branched alkyl) having up to 9 carbon atoms or an alkenyl group (linear and / or branched alkenyl) having up to 9 carbon atoms) can be advantageously synthesized from the 2-substituted acrolein of formula (III) by exposing the acrolein together with hydroxylamine hydrochloride or hydroxylamine sulfate or a hydroxylamine source in the presence of a base such as sodium acetate, potassium acetate or sodium hydroxide in a solvent such as methanol or ethanol at room temperature or under heating, for example at 60°C to 100°C for 4 to 10 hours.

[0066] Substituted 2-methylenenitriles of formula (V) are formed by subjecting the oxime to dehydrating conditions, such as treating the 2-substituted oxime of formula (VI) from the previous step with a suitable dehydrating reagent, such as acetic anhydride, at 110°C to 140°C for 6 to 8 hours.

[0067] In an embodiment according to the invention, the compounds of formula (I) can advantageously be prepared by the following three successive steps: - Formula (IV) [ka] wherein R3 is either an alkyl group (linear and / or branched alkyl) having up to 9 carbon atoms or an alkenyl group (linear and / or branched alkyl) having up to 9 carbon atoms, by reacting with formaldehyde to give an aldehyde of formula (III): [ka] forming an acrolein substituted at the 2-position of R3, wherein R3 is either an alkyl group (linear and / or branched alkyl) having up to 9 carbon atoms or an alkenyl group (linear and / or branched alkyl) having up to 9 carbon atoms; - the acrolein substituted at the 2-position from the previous step is subjected to a reaction step of reduction or nucleophilic addition of an organometallic reagent to give the compound of formula (II) [ka] forming an allylic alcohol substituted at the 2- and / or 1-position of the alkyl group (linear and / or branched alkyl) having up to 9 carbon atoms or the alkenyl group (linear and / or branched alkyl) having up to 9 carbon atoms, and R is a hydrogen atom or an alkyl group (linear and / or branched alkyl) having up to 9 carbon atoms or the alkenyl group (linear and / or branched alkyl) having up to 9 carbon atoms; - the 2- and / or 1-substituted allylic alcohol of formula (II) from the previous step is reacted with a substituted 2-methylenenitrile (V) to give the compound of formula (I) [ka] (wherein R1 is a hydrogen atom or a methyl group; R2 is a hydrogen atom or an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms; R3 is an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms; and R4 is a hydrogen atom or a methyl group, or an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms).

[0068] In an embodiment according to the invention, R2 may advantageously be linear and / or branched alkyl. In an embodiment according to the invention, R3 may advantageously be linear and / or branched alkyl / alkenyl. In an embodiment according to the invention, R4 may advantageously be linear and / or branched alkyl.

[0069] An exemplary scheme for the synthesis of compounds of formula (I) according to the present invention is shown below.

[0070] [ka]

[0071] Here, aldehydes of formula (IV) having two hydrogens at the α-position are converted to substituted acroleins (III) by reaction with formaldehyde (in the form of paraformaldehyde or formalin), which are reduced with sodium borohydride or treated with the Grignard reagent RMgX to give the corresponding substituted allylic alcohols (II). These substituted allylic alcohols (II) are then reacted with substituted 2-methylenenitriles (V or VII) in the presence of KOH / tetra-n-butylammonium bromide in water at 25°C to form compounds of formula (I).

[0072] In an embodiment of the present invention, the aldol condensation, specifically the reaction of an aldehyde with formaldehyde (first preparation step), is carried out in the presence of a catalyst based on boric acid and a secondary amine, preferably diethanolamine. By developing this particular preparation step, the applicants have significantly improved the overall preparation process thanks to the low odor impact of the catalyst compared to other catalyst systems for aldol condensation that use strong-smelling amines, such as diethylamine, dibutylamine, piperidine, or pyrrolidine, or unpleasant-smelling acids, such as fatty acids, and the low catalyst loading compared to similar catalyst systems, such as dibutylamine / hexanoic acid or piperidine / stearic acid. The combination of the availability and low cost of the components of the catalyst system and the relatively low molecular weight of boric acid compared to other acids with similar pKa is particularly advantageous, as it has a beneficial impact on the economics of the methylenation process using this catalyst system. [Example]

[0073] In an embodiment according to the present invention, the fragrance, flavor, and / or deodorizing / masking composition comprises one or more compounds of formula (I) selected from the following synthesized compounds shown below. For each compound, a description of the compound's odor is also provided. ND means not determined.

[0074] [ka]

[0075] [Table 1-1] [Table 1-2]

[0076] The synthesis procedures and characterization data for some selected compounds are given below.

[0077] Example 1 Synthesis of 3-(3-methyl-2-methylenebutoxy)propanenitrile Step 1: Synthesis of 3-methyl-2-methylenebutanal 3-Methylbutanal (200 g, 2.32 mol) was added to a mixture of aqueous formaldehyde (37%) (207 g, 2.55 mol), di-n-butylamine (15.0 g, 0.116 mol), and p-anisic acid (17.6 g, 0.116 mmol) over 2 h at 25 °C, and the reaction mixture was then heated at 70 °C for 4 h. The reaction mixture was cooled to 25 °C, and the organic phase was separated, washed with water (3 × 100 mL), and dried over anhydrous sodium sulfate. Volatiles were removed, and the resulting crude residue was distilled under reduced pressure (42 °C–45 °C / 100 mbar) to give 3-methyl-2-methylenebutanal (167 g, 73%) as a colorless liquid.

[0078] 1 H NMR (400MHz, CDCl3): δ 9.45 (s, 1H), 6.17 (s, 1H), 5.89 (s, 1H), 2.71 (septet, J = 6.8Hz, 1H), 0.99 (d, J = 6.8Hz, 6H). 13 C NMR (100MHz, CDCl3): δ 193.5,155.5,131.1,25.1,20.2.

[0079] Step 2: Synthesis of 3-methyl-2-methylenebutan-1-ol Sodium borohydride (6.94 g, 183 mmol) was added to a stirred mixture of 3-methyl-2-methylenebutanal (60 g, 611 mmol) and water (300 mL) over 15 minutes at 10°C to 15°C. The reaction mixture was then stirred at 25°C for 3 hours. The reaction mixture was subsequently diluted with 10% aqueous hydrochloric acid (100 mL) and extracted with MTBE (2 x 120 mL). The organic phase was separated and washed successively with water (150 mL), 10% aqueous sodium carbonate (150 mL), and brine (150 mL). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give 3-methyl-2-methylenebutan-1-ol, which was used directly in the subsequent step.

[0080] Step 3: Synthesis of 3-(3-methyl-2-methylenebutoxy)propanenitrile To a mixture of 3-methyl-2-methylenebutan-1-ol (20 g, 200 mmol) and 18-crown-6 (1.056 g, 3.99 mmol) in dichloromethane (100 mL) was added a solution of potassium hydroxide (16.80 g, 300 mmol) in water (40 mL). Next, acrylonitrile (15.89 g, 300 mmol) was added over 30 minutes. The reaction mixture was stirred at 25 °C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with methyl tertiary butyl ether (MTBE, 2 × 50 mL). The combined organic layers were washed successively with water (40 mL) and brine (40 mL), and the volatiles were removed under reduced pressure. The residue was purified by distillation (110° C.-112° C. / 5 mbar) to give 3-((3-methylenepentan-2-yl)oxy)propanenitrile (12.0 g, 38%) as a colorless liquid. Scent note: ND.

[0081] 1 H NMR(400MHz,CDCl3):δ 5.01(s,1H),4.96(s,1H),4.03(s,2H),3.63(t,J=6.4Hz,2H),2.62(t,J=6.4Hz,2H),2.35(septet,J=6.4Hz,1H),1.07(t,J=7.2Hz,6H). 13C NMR(100MHz, CDCl3)δ 151.2,117.5,109.9,73.3,64.4,30.1,21.3,19.1.

[0082] Example 2 Synthesis of 3-((5-methyl-4-methylenehexan-3-yl)oxy)butanenitrile To a mixture of 5-methyl-4-methylenehexan-3-ol (15 g, 117 mmol), KOH (7.22 g, 129 mmol), and tetra-n-butylammonium bromide (1.886 g, 5.85 mmol) in water (15 mL) at 25 °C was added a solution of (E)-but-2-enenitrile (crotonitrile) (11.77 g, 175 mmol) in dichloromethane (15 mL) over 20 minutes. The reaction mixture was stirred at 25 °C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water (20 mL) and brine (20 mL), and the volatiles were removed under reduced pressure. The resulting residue was purified by distillation (67° C. / 3 mbar) to give 3-((5-methyl-4-methylenehexan-3-yl)oxy)butanenitrile (12 g, 52%) as an inseparable mixture of diastereomers. Scent note: ND.

[0083] 1 H NMR(300MHz,CDCl3):δ 5.02-4.97(m,2H),3.73-3.64(m,2H),2.52-2.44(m,2H),2.23(Septet, J=6.9Hz,1H), 1.60-1.50(m,2H),1.32-1.25(m,3H),1.05(t,J=6.9Hz,6H),0.90(t,J=7.8Hz,3H).

[0084] Example 3 Synthesis of 3-(2-methylenebutoxy)propanenitrile Step 1: Synthesis of 2-methylenebutanal A mixture of n-butyraldehyde (100.0 g, 1.38 mmol), boric acid (0.85 g, 13.87 mmol), formaldehyde (45.8 g, 1.52 mmol), and diethanolamine (15.58 g, 0.14 mmol) was stirred at 32 °C for 18 h. The reaction mixture was diluted with dilute HCl (50 mL) and subsequently washed with aqueous sodium carbonate (50 mL). The organic layer was extracted with ethyl acetate (3 × 100 mL). The combined organic layers were washed with brine (100 mL), dried over anhydrous sodium sulfate, and the resulting solution was concentrated under reduced pressure. The resulting residue was purified by distillation to give 2-methylenebutanal (60.0 g, 51%) as a colorless liquid.

[0085] 1 H NMR (400MHz, CDCl3): δ 9.45 (s, 1H), 6.15 (s, 1H), 5.89 (s, 1H), 2.18-2.12 (m, 2H), 0.96 (t, J = 7.6Hz, 3H). 13 C NMR (75MHz, CDCl3): δ 194.7,151.7,133.1,20.8,11.8.

[0086] Step 2: Synthesis of 2-methylenebutan-1-ol Sodium borohydride (2.06 g, 57.7 mmol) was added to a stirred mixture of 2-methylenebutanal (23 g, 273 mmol) and water (30 mL) over 15 minutes at 10°C to 15°C. The reaction mixture was then stirred at 25°C for 3 hours. The reaction mixture was subsequently diluted with 10% aqueous hydrochloric acid (60 mL). The organic phase was separated and washed successively with water (60 mL), 10% aqueous sodium carbonate (60 mL), and brine (60 mL). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give 2-methylenebutan-1-ol, which was used directly in the subsequent step.

[0087] 1H NMR (300MHz, CDCl3): δ 5.00(s,1H),4.87(s,1H),4.08(s,2H),2.09(q,J=7.5Hz,2H),1.89(wide s,1H),1.07(t,J=7.5Hz,3H). 13 C NMR (75MHz, CDCl3): δ 150.8,108.0,65.9,25.7,12.2.

[0088] Step 3: Synthesis of 3-(2-methylenebutoxy)propanenitrile To a mixture of 2-methylenebutan-1-ol (15.0 g, 174 mmol), KOH (10.75 g, 192 mmol), and tetra-n-butylammonium bromide (2.80 g, 8.71 mmol) in water (30 mL) at 25 °C, a solution of acrylonitrile (13.86 g, 261 mmol) in dichloromethane (15 mL) was added over 20 min. The reaction mixture was stirred at 25 °C for 15 h. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water (20 mL) and brine (20 mL), and the volatiles were removed under reduced pressure. The residue was purified by distillation to give pure 3-(2-methylenebutoxy)propanenitrile (9.0 g, 37%) as a colorless liquid. Scent note: ND.

[0089] 1 H NMR(400MHz,CDCl3):δ 4.74(s,1H),4.67(s,1H),3.72(s,2H),3.35(t,J=6.4Hz,2H),2.35(t,J=6.4Hz,2H),1.81(q,J=7.6Hz,2H),0.80(t,J=7.6Hz,3H). 13 C NMR (100MHz, CDCl3): δ 146.9,117.9,111.0,74.3,65.2,25.7,18.8,11.9.

[0090] Example 8 Synthesis of 3-((4-methylenehexan-3-yl)oxy)butanenitrile To a mixture of 4-methylenehexan-3-ol (4.0 g, 35.03 mmol), KOH (1.9 g, 33.86 mmol), water (10 mL), and 18-crown-6 (0.18 g, 0.68 mmol) at 25 °C, a solution of (E)-but-2-enenitrile (2.8 g, 41.73 mmol) in dichloromethane (7 mL) was added over 20 min. The reaction mixture was stirred at 25 °C for 15 h. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water (20 mL) and brine (20 mL), and the volatiles were removed under reduced pressure. The residue was purified by distillation to give 3-((4-methylenehexan-3-yl)oxy)butanenitrile (2.8 g, 50%) as a colorless liquid. Odor notes: Earthy, dry notes.

[0091] 1 H NMR(300MHz,CDCl3):δ 4.98(s,1H),4.93(s,1H),3.76-3.65(m,2H),2.54-2.45(m,2H),2.15-1.90(m,2H) ,1.651.49(m,2H),1.33-1.24(m,3H),1.07(t,J=7.2Hz,3H),0.87(t,J=7.5Hz,3H).

[0092] Example 9 Synthesis of 3-((2-methylenepentyl)oxy)propanenitrile Step 1: Synthesis of 2-methylenepentanal A 250 mL round-bottom flask equipped with a reflux condenser was charged with di-n-butylamine (1.88 g, 14.51 mmol), acetic acid (1.66 mL, 29.0 mmol), and aqueous formaldehyde (25.9 mL, 37% solution in water, 348 mmol). The resulting solution was heated to 50°C over 10 minutes with stirring. Next, n-pentanal (25.0 g, 290 mmol) was added over 1 hour. A slight exotherm was observed during the addition. After stirring the reaction mixture at 50°C for 16 hours, the reaction mixture was cooled to 25°C. The reaction mixture was washed with 5% HCl (3 x 20 mL). The organic layer was then washed with saturated sodium bicarbonate (30 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by distillation under reduced pressure (50° C.-54° C. / 3 mbar) to give 2-methylenepentanal (10.0 g, 35%) as a colorless liquid.

[0093] 1 H NMR (400MHz, CDCl3): δ 9.47(s,1H),6.18(s,1H),5.93(s,1H),2.15(t,J=7.6Hz,2H),1.46-1.36(m,2H),0.86(t,J=7.6Hz,3H). 13 C NMR (100MHz, CDCl3): δ 198.0,150.0,134.2,29.7,21.0,15.2.

[0094] Step 2: Synthesis of 2-methylenepentan-1-ol Sodium borohydride (1.16 g, 30.6 mmol) was added to a stirred mixture of 2-methylenepentanal (10.0 g, 102 mmol) and water (15 mL) over 15 minutes at 10°C to 15°C. The reaction mixture was then stirred at 25°C for 3 hours. The reaction mixture was subsequently diluted with 10% aqueous hydrochloric acid (20 mL). The organic phase was separated and washed successively with water (25 mL), 10% aqueous sodium carbonate (25 mL), and brine (25 mL). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give 2-methylenepentan-1-ol, which was used directly in the subsequent step.

[0095] Step 3: Synthesis of 3-((2-methylenepentyl)oxy)propanenitrile To a mixture of 3-methyl-2-methylenebutan-1-ol (20.0 g, 199.7 mmol), KOH (12.32 g, 219.57 mmol), and tetra-n-butylammonium bromide (3.22 g, 9.98 mmol) in water (30 mL) at 25 °C, a solution of acrylonitrile (15.97 g, 19.72 mL, 301 mmol) in dichloromethane (15 mL) was added over 20 minutes. The reaction mixture was stirred at 25 °C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water (30 mL) and brine (30 mL), and the volatiles were removed under reduced pressure. The residue was purified by distillation (56-60° C. at 3 mbar) to give pure 3-((2-methylenepentyl)oxy)propanenitrile (13.8 g, 45%) as a colorless liquid. Scent note: ND.

[0096] 1 H NMR(400MHz,CDCl3):δ 5.03(s,1H),4.90(s,1H),3.98(s,2H),3.64(t,J=6.4Hz,2H),2.63(t,J=6 .4Hz,2H),2.05(t,J=7.6Hz,2H),1.54-1.45(m,2H),0.94(t,J=7.2Hz,3H). 13 C NMR (100MHz, CDCl3): δ 145.2,118.0,112.4,74.0,64.4,35.6,20.4,19.1,13.8.

[0097] Example 10 Synthesis of 3-((3-methylenehexan-2-yl)oxy)propanenitrile Step 1: Synthesis of 3-methylenehexan-2-ol To a cooled (0°C) solution of 2-methylenepentanal (30 g, 306 mmol) in THF (120 mL) was slowly added a solution of methylmagnesium chloride (153 mL, 3 M in tetrahydrofuran, 459 mmol). The reaction mixture was stirred at room temperature for 4 hours. After the reaction was complete, the reaction mixture was diluted with ammonium chloride solution (50 mL). The solution was extracted with ethyl acetate (3 x 50 mL). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The crude product was distilled to give 3-methylenehexan-2-ol (20 g, 57%).

[0098] 1 H NMR(400MHz,CDCl3):δ 4.97(s,1H),4.73(s,1H),4.17(q,J=6.4Hz,1H),2.04-1.88(m,2H),1.84 (s,1H),1.47-1.38(m,2H),1.21(d,J=6.4Hz,3H),0.86(t,J=7.2Hz,3H), 13 C NMR (100MHz, CDCl3): δ 153.2,108.3,70.6,33.2,21.9,21.3,13.9.

[0099] Step 2: Synthesis of 3-((3-methylenehexan-2-yl)oxy)propanenitrile To a mixture of 3-methylenehexan-2-ol (10.0 g, 88 mmol), KOH (5.40 g, 96 mmol), and tetra-n-butylammonium bromide (1.41 g, 4.38 mmol) in water (15 mL) at 25 °C was added a solution of acrylonitrile (8.65 mL, 131 mmol) in dichloromethane (10 mL) over 20 minutes. The reaction mixture was stirred at 25 °C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (40 mL). The combined organic layers were washed successively with water (30 mL) and brine (30 mL). The volatiles were removed under reduced pressure, and the resulting residue was distilled under reduced pressure (65 °C-67 °C at 3 mbar) to give 3-((3-methylenehexan-2-yl)oxy)propanenitrile (8.0 g, 54%) as a colorless liquid. Odor notes: dusty, woody, earthy, patchouli-like.

[0100] 1 H NMR(400MHz,CDCl3):δ 4.93(s,1H),4.83(s,1H),3.82-3.78(m,1H),3.56-3.50(m,1H),3.42-3.36(m,1H),2.50(t,J=6 .4Hz,2H),1.91(t,J=8Hz,2H),1.48-1.37(m,2H),1.20(d,J=6.4Hz,3H),0.88(t,J=7.2Hz,3H). 13 C NMR (100MHz, CDCl3): δ 149.4,118.0,112.1,80.0,62.7,32.4,20.7,20.3,18.8,14.0.

[0101] Example 11 Synthesis of 3-((3-methylenehexan-2-yl)oxy)butanenitrile To a mixture of KOH (5.40 g, 96 mmol) and tetra-n-butylammonium bromide (1.41 g, 4.38 mmol) in water was added 3-methylenehexan-1-ol (10.0 g, 88 mmol) over 15 minutes at 30 °C, followed by the addition of a solution of (E)-but-2-enenitrile (8.81 g, 131 mmol) in dichloromethane (10 mL) over 30 minutes at 30 °C. The reaction mixture was stirred at 25 °C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (40 mL). The combined organic layers were washed successively with water and brine. Volatiles were removed under reduced pressure. The crude product was purified by fractional distillation under reduced pressure (71 °C-74 °C at 3 mbar) to give the pure product (E)-but-2-enenitrile (8.81 g, 50%) as a colorless liquid. Odor notes: Dry, dusty, earthy, rooty.

[0102] Example 12 Synthesis of 3-((4-methyleneheptan-3-yl)oxy)propanenitrile Step 1: Synthesis of 4-methyleneheptan-3-ol 2-Methylenepentanal (40 g, 408 mmol) was taken up in THF (120 mL) and cooled to 0 °C. A cold solution of ethylmagnesium chloride (245 mL, 2 M in THF, 489 mmol) was added over 15 minutes. The reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was then diluted with saturated ammonium chloride solution (50 mL), and the mixture was extracted with ethyl acetate (3 × 100 mL). The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The resulting crude product was purified by distillation under reduced pressure (3 mbar and 40 °C) to give 4-methyleneheptan-3-ol (14 g, 26%) as a colorless liquid.

[0103] 1 H NMR (400MHz, CDCl3): δ 5.01(s,1H),4.85(s,1H),4.0(t,J=6.4Hz,1H),2.09-1.68(m,2H),1.66-1.43(m,4H),0.96-0.89(m,6H). 13 C NMR (100MHz, CDCl3): δ 150.6,108.4,75.7,33.1,27.3,20.1,12.8,9.6.

[0104] Step 2: Synthesis of 3-((4-methyleneheptan-3-yl)oxy)propanenitrile To a mixture of 4-methyleneheptan-3-ol (7 g, 54.6 mmol), KOH (3.37 g, 60.1 mmol), and tetra-n-butylammonium bromide (0.88 g, 2.73 mmol) in water (20 mL) at 25 °C was added a solution of acrylonitrile (5.39 mL, 82 mmol) in dichloromethane (8 mL) over 20 min. The reaction mixture was stirred at 25 °C for 15 h. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (40 mL). The combined organic layers were washed successively with water and brine. The volatiles were removed under reduced pressure, and the resulting residue was distilled under reduced pressure (74 °C-76 °C at 3 mbar) to give 3-((4-methyleneheptan-3-yl)oxy)propanenitrile (6.0 g, 60%) as a colorless liquid. Odor notes: Dry dusty notes.

[0105] 1 H NMR(400MHz,CDCl3):δ 4.91-(s,1H),4.88-4.87(m,1H),3.60-3.49(m,2H),3.39-3.32(m,1H),2.50(t,J=6.4Hz ,2H),1.89-1.83(m,2H),1.60-1.42(m,4H),0.87(t,J=7.2Hz,3H),0.82(t,J=7.2Hz,3H). 13 C NMR (100MHz, CDCl3): δ 147.9,118.1,112.2,86.3,62.8,32.1,26.9,18.8,13.8,10.2.

[0106] Example 13 Synthesis of 3-((2-methylenehexyl)oxy)propanenitrile Step 1: Synthesis of 2-methylenehexanal n-Hexanal (3.88 kg, 38.7 mol, 1 equiv.) was added over 2 h with stirring at 10-15 °C to a mixture of 37% aqueous formaldehyde (3.7 kg, 46.5 mol, 1.2 equiv.), di-n-butylamine (252 g, 1.95 mol, 0.05 equiv.), and p-anisic acid (295 g, 1.9 mol, 0.05 equiv.). After the addition was complete, the reaction mixture was stirred at 50 °C for 2 h. The reaction mixture was then cooled to 25 °C. The organic phase was separated, washed with water (3 × 2 L), and dried over anhydrous sodium sulfate (250 g). The crude product was distilled (45-49 °C / 53 mbar) to give 2-methylenehexanal (3.98 kg, 91%) as a colorless liquid.

[0107] 1 H NMR (400MHz, CDCl3): δ 9.45(s,1H),6.17(s,1H),5.91(s,1H),2.17-2.13(m2H),1.38-1.20(m,4H),0.82(t,J=7.2Hz,3H). 13 C NMR (100MHz, CDCl3): δ 194.5,150.5,133.7,29.9,27.3,22.0,13.6.

[0108] Step 2: Synthesis of 2-methylenehexan-1-ol Sodium borohydride (383 g, 10.1 mol, 0.272 equiv.) was added to a mixture of 2-methylenehexanal (4.18 kg, 37.3 mol, 1 equiv.) and water (5.60 L) over 4 h with stirring at 10-15 °C. The reaction mixture was then stirred at 25 °C for 3 h. The reaction mixture was subsequently diluted with aqueous hydrogen chloride (10%, 3 L). The organic phase was separated and washed successively with water (3 L), 10% aqueous sodium carbonate (3 L), and brine (3 L). The organic phase (4.13 kg) was distilled under reduced pressure (52-54 °C / 4 mbar) to give 2-methylenehexan-1-ol (3.94 kg, 92%) as a colorless liquid.

[0109] 1 H NMR (400MHz, CDCl3): δ 5.00(m,1H),4.86-4.85(m,1H),4.05(s,2H),2.07-2.03(m,3H),1.47-1.30(m,4H),0.91(t,J=7.2Hz,3H). 13 C NMR (100MHz, CDCl3): δ 149.0,108.6,65.4,35.6,32.8,22.6,13.8.

[0110] Step 3: Synthesis of 3-((2-methylenehexyl)oxy)propanenitrile To a mixture of 2-methylenehexan-1-ol (250 g, 2.06 mol), potassium hydroxide (127 g, 2.26 mol), and tetra-n-butylammonium bromide (33.2 g, 0.10 mol) in water (375 mL) at 25 °C, acrylonitrile (164.0 g, 3.08 mmol) was added over 2 h. The reaction mixture was stirred at 25 °C for 5 h. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was washed successively with water (3 × 200 mL) and brine (2 × 200 mL). The residue (315 g) was distilled under reduced pressure (85 °C-90 °C / 3 mbar) to give 3-((2-methylenehexyl)oxy)propanenitrile (256 g, 70%) as a colorless liquid. Odor notes: Intense woody, coriander, aldehydic, citrus, mandarin, pear, cinnamon, petal floral.

[0111] 1 H NMR(400MHz,CDCl3):4.98(s,1H),4.89(s,1H),3.94(s,2H),3.58(t,J=6.0Hz,2H),2.58(t,J=6.0Hz,2H),2.02(t,J=7.6Hz,2H),1.44-1.25(m,4H),δ 0.88(t,J=7.6Hz,3H). 13 C NMR (100MHz, CDCl3): δ 145.4,117.9,111.8,74.0,64.5,32.6,29.5,18.8,16.0,14.0.

[0112] Example 14 Synthesis of 3-((2-methylenehexyl)oxy)butanenitrile To a mixture of 2-methylenehexan-1-ol (15 g, 131 mmol), potassium hydroxide (8.11 g, 144 mmol), and tetra-n-butylammonium bromide (2.11 g, 6.57 mmol) in water (32 mL) at 25 °C, a solution of (E)-but-2-enenitrile (13.22 g, 197 mmol) in dichloromethane (15 mL) was added over 30 min. The reaction mixture was stirred at 25 °C for 28 h. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, washed successively with water (40 mL), brine (40 mL), and concentrated. The residue was distilled under reduced pressure (88 °C-90 °C / 3 mbar) to give 3-((2-methylenehexyl)oxy)butanenitrile (16.9 g, 71%) as a colorless liquid. Scent note: ND.

[0113] 1H NMR(400MHz,CDCl3):δ 4.95(s,1H),4.83(s,1H),3.90(d,J=12.4Hz,1H),3.85(d,J=12.4Hz,1H),3.72-3.65(m,1H),2.45 (d,J=5.6Hz,2H),2.01-1.96(m,2H),1.40-1.31(m,2H),1.28-1.21(m,5H),0.84(t,J=7.2Hz,3H). 13 C NMR (100MHz, CDCl3): δ 145.8,117.6,111.6,71.8,70.2,31.2,29.6,25.3,23.1,18.7,14.4.

[0114] Example 15 Synthesis of 3-((4-methyleneoctan-3-yl)oxy)propanenitrile A solution of 4-methyleneoctan-3-ol (15.0 g, 105 mmol), potassium hydroxide (7.69 g, 137 mmol), and tetra-n-butylammonium bromide (1.7 g, 5.27 mmol) in water (60 mL) was stirred at room temperature for 30 minutes. Next, a solution of acrylonitrile (7.27 g, 137 mmol) in dichloromethane (10 mL) was slowly added to the mixture, and the reaction was continued at room temperature for 16 hours. The reaction mixture was acidified with dilute HCl to a pH of 3-4. The organic layer was separated, washed with water (20 mL), dried over anhydrous sodium sulfate, and concentrated. The residue was distilled under reduced pressure (82 °C and 3 mbar) to give 3-((4-methyleneoctan-3-yl)oxy)propanenitrile (11.5 g, 55%) as a colorless liquid. Scent note: ND.

[0115] 1 H NMR(300MHz,CDCl3):δ 4.97-4.93(m,2H),3.66-3.55(m,2H),3.46-3.38(m,1H),2.55(t,J=6.3Hz,2H),1.98-1.91(m,2H),1.62-1.31(m,6H),0.94-0.86(m,6H). 13C NMR (75MHz, CDCl3): δ 148.1,118.0,111.9,62.8,29.9,29.6,26.9,22.6,18.9,86.3,13.9,10.2.

[0116] Example 16 Synthesis of 3-((4-methyleneoctan-3-yl)oxy)butanenitrile To a solution of 4-methyleneoctan-3-ol (15.0 g, 105 mmol) and tetra-n-butylammonium bromide (1.70 g, 5.27 mmol) in dichloromethane (36 mL), a solution of potassium hydroxide (7.69 g, 137 mmol) dissolved in water (9 mL) was slowly added, and the reaction mixture was stirred for 15 minutes. Next, crotonitrile (8.49 g, 127 mmol) was added to the mixture over 30 minutes. After the reaction was complete, the reaction mixture was acidified with dilute HCl (pH approximately 3-4), and the organic layer was separated. The organic layer was washed with water (40 mL), dried, and concentrated. The crude material was purified under reduced pressure (87 °C / 3 mbar) to give 3-((4-methyleneoctan-3-yl)oxy)butanenitrile (18.5 g, 84%) as an inseparable mixture of diastereomers. Scent note: ND.

[0117] 1 H NMR(300MHz,CDCl3):δ 4.97(s,1H),4.91(s,1H),3.72-3.64(m,2H),2.48-2.43(m,2H),2.05-1 .94(m,2H),1.56-1.30(m,6H),1.26(t,J=6.6Hz,3H),0.94-0.84(m,6H).

[0118] Example 17 Synthesis of 3-((2-methyleneheptyl)oxy)propanenitrile Step 1: Synthesis of 2-methyleneheptanal Heptanal (160 g, 1.40 mol) was added to a mixture of aqueous formaldehyde (37%) (136 g, 1.68 mol), di-n-butylamine (9.06 g, 0.07 mol), and acetic acid (8.02 mL, 0.14 mol) over 30 min at 25 °C, and the reaction mixture was then heated at 60 °C for 4 h. The reaction mixture was cooled to 25 °C, and the organic phase was separated and washed successively with aqueous NaHCO (50 mL), water (50 mL), and dried over anhydrous sodium sulfate. Volatiles were removed under reduced pressure to give 2-methyleneheptanal (145 g, 1.15 mol, 82%) as a colorless liquid. The crude product was used directly in further reactions.

[0119] 1 H NMR (400MHz, CDCl3): δ 9.46(s,1H),6.18(s,1H),5.92(s,1H),2.16(t,J=7.2Hz,2H),1.41-1.34(m,2H),1.30-1.19(m,4H),0.81(t,J=7.2Hz,3H). 13 C NMR (100MHz, CDCl3): δ 194.8,150.4,133.9,31.4,27.7,27.4,22.2,13.9.

[0120] Step 2: Synthesis of 2-methyleneheptan-1-ol Sodium borohydride (5.40 g, 0.143 mol) was added to a stirred mixture of 2-methyleneheptanal (45 g, 0.36 mol) and water (120 mL) over 15 minutes at 10°C to 15°C. The reaction mixture was then stirred at 25°C for 3 hours. The reaction mixture was subsequently diluted with 10% aqueous hydrochloric acid (50 mL). The organic phase was separated, and the aqueous layer was extracted with MTBE (2 x 50 mL). The combined organic layers were washed successively with water (50 mL), 10% aqueous sodium carbonate (50 mL), and brine (50 mL). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give 2-methyleneheptan-1-ol (42 g, 92%), which was used directly in the subsequent step.

[0121] 1H NMR(400MHz,CDCl3):δ 4.99(s,1H),4.84(s,1H),4.04(s,2H),2.56(wide s,1H),2.03(t,J=7.6Hz,2H),1.48-1.40(m,2H),1.37-1.23(m,4H),0.89(t,J=7.2Hz,3H). 13 C NMR (100MHz, CDCl3): δ 149.2,108.8,65.7,32.9,31.4,27.6,22.6,14.0.

[0122] Step 3: Synthesis of 3-((2-methyleneheptyl)oxy)propanenitrile To a mixture of 2-methyleneheptan-1-ol (14 g, 109.19 mmol), KOH (7.35 g, 131 mmol), and tetra-n-butylammonium bromide (1.76 g, 5.46 mmol) in water (30 mL) at 25 °C, acrylonitrile (8.73 g, 10.78 mL, 16.46 mmol) was added over 20 minutes. The reaction mixture was stirred at 25 °C for 15 hours. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water (20 mL) and brine (20 mL), and the volatiles were removed under reduced pressure. The residue was purified by distillation (90 °C / 4 mbar) to give 3-((2-methyleneheptyl)oxy)propanenitrile (5.2 g, 30%) as a colorless liquid. Scent note: ND.

[0123] 1 H NMR(400MHz,CDCl3):δ 5.02(s,1H),4.95(s,1H),3.98(s,2H),3.64(t,J=6.4Hz,2H),2.63(t,J=6.4Hz,2H) ,2.06(t,J=8.0Hz,2H),1.50-1.45(m,2H),1.45-1.25(m,4H),0.91(t,J=6.8Hz,3H). 13 C NMR (100MHz, CDCl3): δ 145.5,117.9,111.9,73.8,64.4,32.7,31.5,27.3,22.6,18.8,13.8.

[0124] Example 18 Synthesis of 3-((2-methyleneheptyl)oxy)butanenitrile To a mixture of 2-methyleneheptan-1-ol (12 g, 93.58 mmol), KOH (7.88 g, 140.4 mmol), and tetra-n-butylammonium bromide (1.51 g, 4.68 mmol) in water (30 mL) at 25 °C, (E)-but-2-enenitrile (8.16 g, 9.91 mL, 121.7 mmol) was added over 20 min. The reaction mixture was stirred at 25 °C for 15 h. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water (20 mL) and brine (20 mL), and the volatiles were removed under reduced pressure. The residue was purified by distillation (92 °C / 3 mbar) to give 3-((2-methyleneheptyl)oxy)butanenitrile (3.7 g, 20%) as a colorless liquid. Scent note: ND.

[0125] 1 H NMR(400MHz,CDCl3):δ 5.01(s,1H),4.90(s,1H),3.97,3.92(ABq,J AB = 12.4Hz, 2H), 3.79-3.72 (m, 1H), 2.52 (d, J = 5.6Hz, 2H), 2.05 (t, J = 7.6Hz, 2H), 1.48-1.40 (m, 2H), 1.43-1.23 (overlapped signals, 7H), 0.89 (t, J = 6.8Hz, 3H). 13 C NMR (100MHz, CDCl3): δ 145.8,117.4,111.9,71.8,70.6,32.8,31.8,27.6,25.6,22.6,19.5,14.2.

[0126] Example 19 Synthesis of 3-((3-methyleneoctan-2-yl)oxy)propanenitrile Step 1: Synthesis of 3-methyleneoctan-2-ol To a solution of 2-methyleneheptanal (45 g, 357 mmol) in tetrahydrofuran (120 mL) at 0 °C, methylmagnesium chloride (166 mL, 498 mmol, 3 M in THF) was added over 45 min. After stirring the reaction mixture at 25 °C for 4 h, the reaction mixture was diluted with saturated aqueous ammonium chloride (40 mL), and the entire mixture was extracted with ethyl acetate (3 × 50 mL). The combined organic layers were washed with saturated brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was then distilled under reduced pressure (61 °C–63 °C / 4 mbar–5 mbar) to give 3-methyleneoctan-2-ol (39 g, 77%) as a colorless liquid.

[0127] 1 H NMR (400 MHz, CDCl3): δ 4.94 (s, 1H), 4.70 (s, 1H), 4.14 (q, J = 6.4 Hz, 1H), 2.82 (broad s, 1H), 2.04-1.87 (m, 2H), 1.42-1.35 (m, 2H), 1.27-1.18 (overlapping signals, 7H), 0.82 (t, J = 6.8 Hz, 3H). 13 C NMR (100MHz, CDCl3): δ 153.4,107.7,70.6,31.7,31.4,27.6,22.7,22.3,13.6.

[0128] Step 2: Synthesis of 3-((3-methyleneoctan-2-yl)oxy)propanenitrile To a mixture of 3-methyleneoctan-2-ol (14 g, 98.42 mmol), KOH (6.63 g, 118.16 mmol), and tetra-n-butylammonium bromide (1.51 g, 4.68 mmol) in water (40 mL) at 25 °C, acrylonitrile (7.87 g, 9.72 mL, 148.32 mmol) was added over 20 minutes. The reaction mixture was stirred at 25 °C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water (20 mL) and brine (20 mL), and the volatiles were removed under reduced pressure. The residue was purified by distillation (82° C.-85° C. / 3 mbar) to give 3-((3-methyleneoctan-2-yl)oxy)propanenitrile (12.6 g, 65%) as a colorless liquid. Odor notes: Dry earthy, dusty.

[0129] 1 H NMR(400MHz,CDCl3):δ 4.91(s,1H),4.80(d,J=1.6Hz,1H),3.78(q,J=6.4Hz,1H),3.52-3.46(m,1H),3.38-3.33(m,1H),2.47(t,J=6.4 Hz,2H),1.93-1.88(m,2H),1.42-1.34(m,2H),1.29-1.19(m,4H),1.16(d,J=6.4Hz,3H),0.81(t,J=6.8Hz,3H). 13 C NMR (100MHz, CDCl3): δ 149.8,118.1,110.6,79.6,62.6,31.7,30.3,27.4,22.4,20.3,18.9,13.6.

[0130] Example 20 Synthesis of 3-((3-methyleneoctan-2-yl)oxy)butanenitrile To a mixture of 3-methyleneoctan-2-ol (12 g, 84.36 mmol), KOH (7.10 g, 126.54 mmol), and tetra-n-butylammonium bromide (1.360 g, 4.22 mmol) in water (40 mL) at 25 °C, (E)-but-2-enenitrile (7.36 g, 8.93 mL, 109.7 mmol) was added over 20 minutes. The reaction mixture was stirred at 25 °C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water (20 mL) and brine (20 mL), and the volatiles were removed under reduced pressure. The residue was purified by distillation (82° C.-88° C. / 3 mbar) to give 3-((3-methyleneoctan-2-yl)oxy)butanenitrile (14.8 g, 66%) as an inseparable 6:4 mixture of two diastereomers. Odor notes: Dry, fishy, ​​aqua, ozonic.

[0131] 1 H NMR (400 MHz, CDCl): δ 4.94-4.93 (m, 1H), 4.81-4.79 (m, 1H), 3.93-3.87 (m, 1H), 3.69-3.60 (m, 1H), 2.43-2.37 (m, 2H), 2.01-1.86 (m, 2H), 1.45-1.35 (m, 2H), 1.27-1.23 (m, 3H), 1.20-1.12 (overlapping signals, 7H), 0.83 (t, J = 6.8 Hz, 3H).

[0132] Example 21 Synthesis of 3-((4-methylenenonan-3-yl)oxy)propanenitrile Step 1: Synthesis of 4-methylenenonan-3-ol To a solution of 2-methyleneheptanal (55 g, 435.8 mmol) in tetrahydrofuran (45 mL) at 0° C., ethylmagnesium chloride (283 mL, 566 mmol, 2 M in THF) was added over 25 min. After stirring the reaction mixture at 25° C. for 4 h, the reaction mixture was diluted with saturated aqueous ammonium chloride solution (40 mL). The resulting precipitate was filtered off and washed with EtOAc (150 mL). The combined organic layers were washed with saturated brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by distillation (65° C.-70° C. / 4 mbar) to give 4-methylenenonan-3-ol (28 g, 41%) as a colorless liquid.

[0133] Step 2: Synthesis of 3-((4-methylenenonan-3-yl)oxy)propanenitrile To a mixture of 4-methylenenonan-3-ol (10 g, 64 mmol), potassium hydroxide (5.39 g, 96.06 mmol), and tetra-n-butylammonium bromide (1.031 g, 3.2 mmol) in water (30 mL) at 25 °C was added a solution of acrylonitrile (4.41 g, 5.45 mL, 83.11 mmol) in dichloromethane (8 mL) over 20 minutes. The reaction mixture was stirred at 25 °C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water (20 mL) and brine (20 mL), and the volatiles were removed under reduced pressure. The residue was purified by distillation (98° C.-102° C. / 3 mbar) to give 3-((4-methylenenonan-3-yl)oxy)propanenitrile (7.88 g, 59% yield) as a colorless liquid. Odor notes: Dry, earthy, dusty.

[0134] 1H NMR (400 MHz, CDCl): δ 4.91 (s, 1H), 4.87-4.86 (m, 1H), 3.58-3.50 (m, 2H), 3.36-3.32 (m, 1H), 2.49 (t, J = 6.4 Hz, 2H), 2.0-1.8 (m, 2H), 1.58-1.44 (m, 2H), 1.43-1.33 (m, 2H), 1.31-1.18 (m, 4H), 0.87-0.80 (two overlapping t, 6H). 13 C NMR (100MHz, CDCl3): δ 148.2,118.0,112.3,86.3,62.8,31.8,29.9,27.7,27.4,22.5,19.0,13.5,10.0.

[0135] Example 22 Synthesis of 3-((4-methylenenonan-3-yl)oxy)butanenitrile To a mixture of 4-methylenenonan-3-ol (10 g, 64 mmol), potassium hydroxide (5.39 g, 96.06 mmol), and tetra-n-butylammonium bromide (1.031 g, 3.2 mmol) in water (30 mL) at 25 °C, (E)-but-2-enenitrile (5.58 g, 6.77 mL, 83.17 mmol) was added over 20 minutes. The reaction mixture was stirred at 25 °C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water (20 mL) and brine (20 mL), and the volatiles were removed under reduced pressure. The residue was purified by fractional distillation (88 °C / 3 mbar) to give 3-((4-methylenenonan-3-yl)oxy)butanenitrile (0.89 g, 6% yield) as an inseparable 64:36 mixture of diastereomers. Unreacted 4-methylenenonan-3-ol (9 g) was recovered. Scent note: ND.

[0136] 1H NMR (400 MHz, CDCl): δ 4.91 (s, 1H), 4.86-4.85 (s, 1H), 3.66-3.57 (m, 2H), 2.43-2.38 (m, 2H), 1.95-1.85 (m, 2H), 1.58-1.33 (m, 4H), 1.30-1.17 (overlapping signals, 7H), 0.85-0.80 (two overlapping signals, 6H).

[0137] Example 23 Synthesis of 3-((2-methyleneoctyl)oxy)butanenitrile Prepared from 2-methyleneoctan-1-ol and (E)-but-2-enenitrile by the same procedure as in Example 30. Scent note: ND.

[0138] 1 H NMR(400MHz,CDCl3):δ 5.00(s,1H),4.89(s,1H),3.96,3.91(ABq,J AB = 12.4 Hz, 2H), 3.74 (sextet, J = 6.0 Hz, 1H), 2.51 (d, J = 5.6 Hz, 2H), 2.04 (t, J = 7.6 Hz, 2H), 1.44-1.39 (m, 2H), 1.33-1.27 (overlapped signals, 9H), 0.87 (t, J = 6.8 Hz, 3H). 13 C NMR (100MHz, CDCl3): δ 145.9,117.4,111.7,71.8,70.2,33.0,31.9,29.1,27.5,24.9,22.6,19.6,14.1.

[0139] Example 25 Synthesis of 3-((4-methylenedecan-3-yl)oxy)propanenitrile Step 1: Synthesis of 4-methylenedecan-3-ol To a solution of 2-methyleneoctanal (60 g, 427.86 mmol) in tetrahydrofuran (200 mL) at 0° C. was added ethylmagnesium chloride (214 mL, 428 mmol, 2 M in THF) over 25 minutes. After stirring the reaction mixture at 25° C. for 4 hours, the reaction mixture was diluted with saturated aqueous ammonium chloride solution (40 mL). The resulting precipitate was filtered off and washed with EtOAc (150 mL). The combined organic layers were washed with saturated brine (100 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting crude product was purified by distillation (70° C. / 4 mbar) to give 4-methylenedecan-3-ol (38.7 g, 53%) as a colorless liquid.

[0140] 1 H NMR (300 MHz, CDCl): δ 4.98 (s, 1H), 4.83 (s, 1H), 3.98 (t, J = 6.3 Hz, 1H), 2.08-1.91 (m, 2H), 1.78 (broad s, 1H), 1.63-1.51 (m, 2H), 1.49-1.39 (m, 2H), 1.35-1.27 (overlapping signals, 6H), 0.83-0.91 (overlapping t, 6H). 13 C NMR (75MHz, CDCl3): δ 152.0,109.4,33.1,31.9,31.4,29.4,28.3,27.8,22.7,14.2,9.9.

[0141] Step 2: Synthesis of 3-((4-methylenedecan-3-yl)oxy)propanenitrile To a mixture of 4-methylenedecan-3-ol (14 g, 82.21 mmol), potassium hydroxide (6.00 g, 106.93 mmol), and tetra-n-butylammonium bromide (1.325 g, 4.11 mmol) in water (40 mL) at 25 °C was added a solution of acrylonitrile (6.54 g, 123.25 mmol) in dichloromethane (10 mL) over 20 minutes. The reaction mixture was stirred at 25 °C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water (20 mL) and brine (20 mL), and the volatiles were removed under reduced pressure. The residue was purified by distillation (113° C. / 3 mbar) to give 3-((4-methylenedecan-3-yl)oxy)propanenitrile (11.7 g, 63%) as a colorless liquid. Scent note: ND.

[0142] 1 H NMR (300 MHz, CDCl): δ 4.97 (s, 1H), 4.94 (s, 1H), 3.75-3.56 (m, 2H), 3.46-3.39 (m, 1H), 2.56 (t, J = 6.3 Hz, 2H), 1.98-1.91 (m, 2H), 1.67-1.51 (m, 2H), 1.48-1.41 (m, 2H), 1.37-1.29 (m, 6H), 0.89 (overlapped t, 6H). 13 C NMR (75MHz, CDCl3): δ 148.2,118.1,112.0,86.4,62.9,31.8,30.0,29.3,27.7,26.9,22.6,18.9,14.1,10.2.

[0143] Example 26 Synthesis of 3-((4-methylenedecan-3-yl)oxy)butanenitrile To a mixture of 4-methylenedecan-3-ol (14 g, 82.21 mmol), potassium hydroxide (6.92 g, 123.33 mmol), and tetra-n-butylammonium bromide (1.325 g, 4.11 mmol) in water (30 mL) at 25 °C, a solution of (E)-but-2-enenitrile (6.62 g, 98.67 mmol) in dichloromethane (10 mL) was added over 20 minutes. The reaction mixture was stirred at 25 °C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water (20 mL) and brine (20 mL), and the volatiles were removed under reduced pressure. The residue was purified by distillation (113° C. / 3 mbar) to give 3-((4-methylenedecan-3-yl)oxy)butanenitrile (9.8 g, 50%) as an inseparable mixture of diastereomers. Scent note: ND.

[0144] 1 H NMR (300 MHz, CDCl): δ 4.97 (s, 1H), 4.92 (s, 1H), 3.74-3.62 (m, 2H), 2.47-2.43 (m, 2H), 2.01-1.91 (m, 2H), 1.62-1.41 (m, 4H), 1.36-1.25 (overlapped m, 9H), 0.84-0.92 (overlapped t, 6H).

[0145] Example 27 Synthesis of 3-((2-methylenenonyl)oxy)propanenitrile Step 1: Synthesis of 2-methylenenonanal Nonanal (25.0 g, 175.76 mmol) was added to a stirred mixture of 37% aqueous formaldehyde (5.81 g, 15.70 mL, 193.43 mmol), di-n-butylamine (1.136 g, 8.79 mmol), and acetic acid (1.055 g, 17.57 mmol) at 50°C over 1 h. After the addition was complete, the reaction mixture was stirred at 50°C for 2 h and then at room temperature for 15 h. The organic phase was separated, washed with water, and dried over anhydrous sodium sulfate. The crude product was distilled under reduced pressure (48°C-50°C / 4 mbar) to give 2-methylenenonanal (13.0 g, 48%) as a colorless liquid.

[0146] 1 H NMR (400MHz, CDCl3): δ 9.47(s,1H),6.18(s,1H),5.92(s,1H),2.16(t,J=7.6Hz,2H),1.39-1.35(m,2H),1.24-1.19(m,8H),0.80(t,J=6.8Hz,3H). 13 C NMR (100MHz, CDCl3): δ 193.8,149.5,132.8,30.7,28.3,28.0,26.7,21.6,13.1.

[0147] Step 2: Synthesis of 2-methylenenonan-1-ol Sodium borohydride (1.28 g, 33.83 mmol) was added to a stirred mixture of 2-methylenenonanal (13.0 g, 84.28 mmol) and water (300 mL) over 15 minutes at 10°C to 15°C. The reaction mixture was then stirred at 25°C for 3 hours. The reaction mixture was subsequently diluted with 10% aqueous hydrochloric acid (100 mL) and extracted with MTBE (2 x 50 mL). The organic phase was separated and washed successively with water (50 mL), 10% aqueous sodium carbonate (50 mL), and brine (50 mL). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure to give 2-methylenenonan-1-ol (13.0 g, 98%), which was used directly in the subsequent step.

[0148] 1H NMR(400MHz,CDCl3):δ 4.93(s,1H),4.79(s,1H),4.01(s,2H),1.98(t,J=8.0Hz,2H),1.60(s,1H),1.41-1.34(m,2H),1.30-1.16(m,8H),0.81(t,J=6.4Hz,3H). 13 C NMR (100MHz, CDCl3): δ 149.2,108.8,65.6,33.1,31.8,29.7,29.1,27.7,22.4,14.0.

[0149] Step 3: Synthesis of 3-((2-methylenenonyl)oxy)propanenitrile To a mixture of 2-methylenenonan-1-ol (13.0 g, 83.18 mmol), potassium hydroxide (5.13 g, 91.42 mmol), and tetra-n-butylammonium bromide (1.341 g, 4.16 mmol) in water (20 mL) at 25 °C, a solution of acrylonitrile (6.66 g, 8.22 mL, 125.48 mmol) in dichloromethane (10 mL) was added over 20 minutes. The reaction mixture was stirred at 25 °C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water (20 mL) and brine (20 mL), and the volatiles were removed under reduced pressure. The residue was purified by distillation (98° C.-100° C. / 3 mbar) to give 3-((2-methylenenonyl)oxy)propanenitrile (13.8 g, 79%) as a colorless liquid. Scent note: ND.

[0150] 1 H NMR (400 MHz, CDCl): δ 5.03 (s, 1H), 4.95 (s, 1H), 3.98 (s, 2H), 3.64 (t, J = 6.4 Hz, 2H), 2.63 (t, J = 6.4 Hz, 2H), 2.06 (t, J = 7.6 Hz, 2H), 1.50-1.44 (m, 2H), 1.33-1.29 (overlapping signals, 8H), 0.90 (t, J = 7.2 Hz, 3H). 13C NMR (100MHz, CDCl3): δ 145.5,117.9,111.9,74.3,64.4,33.3,31.6,29.3,29.1,27.5,22.6,18.8,14.0.

[0151] Example 28 Synthesis of 3-((3-methylenedecan-2-yl)oxy)propanenitrile Step 1: Synthesis of 3-methylenedecan-2-ol A solution of 2-methylenenonanal (50 g, 324.15 mmol) in tetrahydrofuran (200 ml) was cooled to 0 °C, and then a solution of methylmagnesium chloride (162 ml, 3 M in THF, 486 mmol) was added dropwise. The reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was diluted with ammonium chloride solution (200 ml). The solution was extracted with ethyl acetate (3 × 150 ml). The combined organic layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The resulting residue was distilled under reduced pressure (75 °C-77 °C / 3 mbar) to give pure 3-methylenedecan-2-ol (30.0 g, 54%) as a colorless liquid.

[0152] 1 H NMR(400MHz,CDCl3):δ 5.05(s,1H),4.82(s,1H),4.26(q,J=6.4Hz,2H),1.98-2.14(m,2H),1.68 (Wide range s, 1H), 1.44-1.51 (m, 2H), 1.29-1.36 (m, 10H), 0.90 (t, J=6.8Hz, 3H). 13 C NMR (100MHz, CDCl3): δ 153.5,107.8,70.8,31.8,31.7,29.5,29.3,28.0,22.6,22.1,13.8.

[0153] Step 2: Synthesis of 3-((3-methylenedecan-2-yl)oxy)propanenitrile To a solution of 3-methylenedecan-2-ol (13.0 g, 76.33 mmol), KOH (4.71 g, 83.94 mmol), and tetra-n-butylammonium bromide (1.23 g, 3.81 mmol) in water (30 mL) was added slowly a solution of acrylonitrile (6.08 g, 114.59 mmol) in dichloromethane (10 mL) at 25 °C. The reaction mixture was maintained at 30 °C for 15 h. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (2 × 40 mL). The organic layer was separated and washed with water (50 mL) and brine (50 mL). The organic layer was concentrated under pressure and the resulting residue was purified by distillation under reduced pressure (100°C / 2 mbar to 3 mbar) to give the pure product 3-((3-methylenedecan-2-yl)oxy)propanenitrile (6.0 g, 35%). Odor notes: dry, fishy, ​​ozone.

[0154] 1 H NMR(400MHz,CDCl3):δ 4.93(s,1H),4.83(d,J=2.4Hz,1H),3.80(q,J=6.4Hz,1H),3.57-3.50(m,1H),3.42-3.36(m,1H),2.50 (t,J=6.4Hz,2H),1.92(t,J=7.2Hz,2H),1.40-1.35(m,2H),1.24-1.19(m,11H),0.82(t,J=6.8Hz,3H). 13 C NMR (100MHz, CDCl3): δ 149.9,118.2,111.1,80.3,62.9,32.0,30.4,29.7,29.4,28.0,22.8,20.6,19.2,14.3.

[0155] Example 29 Synthesis of 3-((3-methylenedecan-2-yl)oxy)butanenitrile To a mixture of 3-methylenedecan-2-ol (10.0 g, 58.72 mmol), KOH (4.94 g, 88.04 mmol), and tetra-n-butylammonium bromide (0.947 g, 2.94 mmol) in water (15 mL) at 25 °C was added a solution of (E)-but-2-enenitrile (5.12 g, 76.13 mmol) in dichloromethane (8 mL) over 20 minutes. The reaction mixture was stirred at 25 °C for 48 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (2 × 50 mL). The combined organic layers were washed successively with water (50 mL) and brine (50 mL), and the volatiles were removed under reduced pressure. The residue was distilled under reduced pressure (95° C.-100° C. / 3 mbar) to give 3-((3-methylenedecan-2-yl)oxy)butanenitrile (5.0 g, 36%) as an inseparable mixture of diastereomers. Scent note: ND.

[0156] 1 H NMR(400MHz,CDCl3):δ 4.93(s,1H),4.83-4.80(m,1H),3.87-3.93(m,1H),3.72-3.61(m,2H),2.45-2.37(m, 2H),1.96-1.90(m,2H),1.44-1.34(m,2H),1.25-1.16(m,13H),0.82(t,J=7.2Hz,3H).

[0157] Example 32 Synthesis of 3-((2-methyl-5-methylenenonan-4-yl)oxy)propanenitrile Step 1: Synthesis of 2-methyl-5-methylenenonan-4-ol: To a solution of 2-methylenehexanal (20 g, 178 mmol) in tetrahydrofuran (350 mL) cooled to 0 °C, a solution of isobutylmagnesium bromide (107 mL, 214 mmol, 2 M solution in THF) was added over 15 minutes. The reaction mixture was stirred at room temperature for 3 hours. The reaction mixture was then diluted with saturated ammonium chloride solution (50 mL), and the mixture was extracted with ethyl acetate (3 × 100 mL). The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The crude product was purified by column chromatography using 100-200 silica gel with 3% ethyl acetate in hexane as the eluent to give 2-methyl-5-methylenenonan-4-ol (13.0 g, 76 mmol, 42.8%) as a colorless liquid.

[0158] 1 H NMR(300MHz,CDCl3):δ 5.725.86(m,1H),5.09-5.16(m,2H),5.03(s,1H),4.85(d,J=1.2Hz,1H),4.08-4.12(m,1H),2.34-2.3 8(m,1H),2.21-2.31(m,1H),1.92-2.13(m,2H),1.80(s,1H),1.24-1.50(m,4H),0.90(t,J=7.2Hz,3H).

[0159] Step 2: Synthesis of 3-((2-methyl-5-methylenenonan-4-yl)oxy)propanenitrile To a mixture of 2-methyl-5-methylenenonan-4-ol (6 g, 35.2 mmol), KOH (2.174 g, 38.8 mmol), water (12 mL), and tetrabutylammonium bromide (0.57 g, 1.76 mmol) at 25°C, acrylonitrile (2.80 g, 52.8 mmol) was added over 20 minutes. The reaction mixture was stirred at 25°C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (40 mL). The combined organic layers were washed successively with water and brine. The volatiles were removed under reduced pressure, and the resulting residue was distilled under reduced pressure (94-97°C at 0.1 mbar) to give 3-((2-methyl-5-methylenenonan-4-yl)oxy)propanenitrile (2.2 g, 9.85 mmol, 28.0%). Scent note: ND.

[0160] 1 H NMR(300MHz,CDCl3):δ 4.97(s,1H),4.90-4.92(m,1H),3.73(dd,J=8.4Hz and 5.1Hz,1H),3.57-3.64(m,1H),3.35-3.43(m,1H) ),2.54(t,J=6.3Hz,2H),1.91-1.96(m,2H),1.69-1.73(m,1H),1.24-1.57(m,6H),0.87-0.94(m,9H). 13 C NMR (100MHz, CDCl3): δ 148.8,118.1,111.7,83.3,62.9,43.5,30.0,29.7,24.7,23.1,22.8,22.4,19.0,14.1.

[0161] Example 33 Synthesis of 3-((2-methyl-5-methylenenonan-4-yl)oxy)butanenitrile To a mixture of 2-methyl-5-methylenenonan-4-ol (8 g, 47.0 mmol), KOH (2.90 g, 51.7 mmol), water (12 mL), and tetrabutylammonium bromide (0.757 g, 2.34 mmol) at 25°C, (E)-but-2-enenitrile (4.73 g, 70.5 mmol) was added over 20 minutes. The reaction mixture was stirred at 25°C for 48 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (40 mL). The combined organic layers were washed successively with water and brine. The volatiles were removed under reduced pressure and the resulting residue was distilled on a Kugelrohr under reduced pressure (157°C at 0.1 mbar) to give 3-((2-methyl-5-methylenenonan-4-yl)oxy)butanenitrile (2.0 g, 8.43 mmol, 17.93%) as a colorless liquid. GC purity 99.0%. Scent note: ND.

[0162] 1 H NMR(300MHz,CDCl3):δ 4.98(s,1H),4.89-4.91(m,1H),3.83(dd,J=8.4Hz and 5.4Hz,1H),3.66-3.75(m,1 H),2.42-2.48(m,2H),1.93-1.97(m,2H),1.21-1.70(m,10H),0.84-0.91(m,9H). 13 C NMR (100MHz, CDCl3): δ 149.6,117.8,111.7,81.3,68.3,43.7,30.0,29.6,25.9,24.5,24.1,22.8,22.3,18.9,14.1.

[0163] Example 34 Synthesis of 3-((6-methylenedecan-5-yl)oxy)propanenitrile Step 1: Synthesis of 6-methylenedecan-5-ol To a solution of 2-methylenehexanal (50.0 g, 446 mmol) in tetrahydrofuran cooled to 0 °C, butylmagnesium chloride (267 mL, 535 mmol, 2 M solution in THF) was added over 15 minutes. The reaction mixture was stirred at room temperature for 3 hours. The reaction mixture was then diluted with saturated ammonium chloride solution (50 mL), and the mixture was extracted with ethyl acetate (3 × 100 mL). The organic layer was dried over sodium sulfate and concentrated under reduced pressure. This was purified by column chromatography using 100-200 silica gel with 3% ethyl acetate in hexane as the eluent to give 6-methylenedecan-5-ol (24 g, 141 mmol, 31.6%) as a colorless liquid.

[0164] 1 H NMR(300MHz,CDCl3):δ 4.98(s,1H),4.80-4.82(m,1H),4.04(t,J=6.0Hz,1H),1.90-2.11(m,2H),1.68(wide s,1H),1.22-1.54(m,10H),0.84-1.19(m,6H).

[0165] Step 2: Synthesis of 3-((6-methylenedecan-5-yl)oxy)propanenitrile To a mixture of 6-methylenedecan-5-ol (8.0 g, 47.0 mmol), KOH (2.90 g, 51.7 mmol), water (16 mL), and tetrabutylammonium bromide (0.757 g, 2.34 mmol) at 25 °C, acrylonitrile (3.74 g, 70.5 mmol) was added over 20 min. The reaction mixture was stirred at 25 °C for 15 h. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water and brine. The volatiles were removed under reduced pressure, and the resulting residue was distilled under reduced pressure (90 °C-93 °C at 2 mbar) to give 3-((6-methylenedecan-5-yl)oxy)propanenitrile (2.0 g, 8.95 mmol, 19.06%) as a colorless liquid. GC purity 98.0%. Scent note: ND.

[0166] 1 H NMR(300MHz,CDCl3):δ 4.97(s,1H),4.91(s,1H),3.67-3.73(m,2H),2.44-2.48(m,2H),1.85-2.10(m,2H),1.10-1.62(m,13H),0.83-0.95(m,6H).

[0167] Example 35 Synthesis of 3-((6-methylenedecan-5-yl)oxy)butanenitrile To a mixture of 6-methylenedecan-5-ol (8 g, 47.0 mmol), KOH (2.90 g, 51.7 mmol), water (16 mL), and tetrabutylammonium bromide (0.757 g, 2.349 mmol) at 25 °C, (E)-but-2-enenitrile (4.73 g, 70.5 mmol) was added over 20 min. The reaction mixture was stirred at 25 °C for 15 h. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water and brine. The volatiles were removed under reduced pressure, and the resulting residue was distilled under reduced pressure (90 °C-93 °C at 2 mbar) to give 3-((6-methylenedecan-5-yl)oxy)butanenitrile (2.0 g, 8.43 mmol, 17.93%) as a colorless liquid. GC purity 98.0%. Scent note: Gentle dry note.

[0168] 1 H NMR(300MHz,CDCl3):δ 4.97(s,1H),4.91(s,1H),3.67-3.73(m,2H),2.44-2.48(m,2H),1.85-2.10(m,2H),1.10-1.62(m,13H),0.83-0.95(m,6H).

[0169] Example 36 Synthesis of 2-(((2-methylenehexyl)oxy)methyl)hexanenitrile Synthesis of substituted 2-methylene oximes (VI): The oxime was prepared by heating substituted 2-methylenealdehyde (III) (1 equivalent) with hydroxylamine hydrochloride (1.5 equivalents) in methanol as a base and sodium acetate (1.5 equivalents) at 60-80°C for 4-10 hours. After the reaction was complete, the mixture was cooled to room temperature, and the methanol was removed under reduced pressure on a rotary evaporator. The residue was diluted with diethyl ether and washed with water. The organic layer was dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give the substituted 2-methyleneoxime (VI). The crude product was purified by column chromatography to give the substituted 2-methyleneoxime (VI) (60-80% yield).

[0170] Synthesis of substituted 2-methylenenitriles (V): The substituted 2-methylene oxime (VI) was heated with acetic anhydride (2 equivalents) at 110-140°C for 6-8 hours. After the reaction was complete, the mixture was cooled to room temperature and extracted with diethyl ether. The organic layer was washed with aqueous sodium bicarbonate (twice), dried over sodium sulfate, and the solvent was evaporated under reduced pressure to give the crude nitrile. The crude nitrile was purified by silica gel column chromatography to give the pure substituted 2-methylene nitrile (V). Yields were 25-30%.

[0171] To a mixture of 2-methylenehexan-1-ol (6 g, 52.5 mmol), KOH (3.24 g, 57.8 mmol), water (10 mL), and tetrabutylammonium bromide (0.847 g, 2.63 mmol) at 25 °C, 2-methylenehexanenitrile (8.60 g, 79 mmol) was added over 20 minutes. The reaction mixture was stirred at 25 °C for 48 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (40 mL). The combined organic layers were washed successively with water and brine. The volatiles were removed under reduced pressure, and the resulting residue was distilled under reduced pressure (101 °C at 0.1 mbar) to give 2-(((2-methylenehexyl)oxy)methyl)hexanenitrile (3.8 g, 17.02 mmol, 32.4%) as a colorless liquid. GC purity: 98.0%. Scent note: ND.

[0172] 1 H NMR(300MHz,CDCl3):δ 4.99(s,1H),4.91(s,1H),3.95(s,2H),3.45-3.55(m,2H),2.72-2.81(m,2H),2.04(t,J=7.8Hz,2H),1.24-1.68(m,10H),0.84-0.94(m,6H). 13 C NMR (100MHz, CDCl3): δ 145.6,120.8,112.0,74.4,69.4,32.7,32.6,29.8,29.2,28.7,22.5,22.3,14.0,13.8.

[0173] Example 37 Synthesis of 2-(((2-methylenehexyl)oxy)methyl)pentanenitrile To a mixture of 2-methylenehexan-1-ol (10 g, 88 mmol), KOH (5.40 g, 96 mmol), water (10 mL), and tetrabutylammonium bromide (1.412 g, 4.38 mmol) at 25 °C, 2-methylenepentanenitrile (12.50 g, 131 mmol) was added over 20 minutes. The reaction mixture was stirred at 25 °C for 15 hours. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (50 mL). The combined organic layers were washed successively with water and brine. The volatiles were removed under reduced pressure, and the resulting residue was distilled under reduced pressure (98 °C-101 °C at 2 mbar) to give 2-(((2-methylenehexyl)oxy)methyl)pentanenitrile (3.0 g, 14.33 mmol, 16.36%) as a colorless liquid. GC purity 98.0%. Scent note: ND.

[0174] 1 H NMR(300MHz,CDCl3):δ 5.00(s,1H),4.92(s,1H),3.96(s,2H),3.46-3.56(m,2H),2.75-2.82(m,1H),2.05(t,J=7.8Hz,2H),1.25-1.68(m,8H),0.82-0.97(m,6H).13 C NMR (100MHz, CDCl3): δ 145.6,120.8,112.0,74.4,69.4,32.8,32.4,31.0,29.8,22.5,20.3,14.0,13.6.

[0175] Example 38 Synthesis of 3-methyl-2-(((2-methylenehexyl)oxy)methyl)butanenitrile To a mixture of 2-methylenehexan-1-ol (6 g, 52.5 mmol), KOH (3.24 g, 57.8 mmol), water (10 mL), and tetrabutylammonium bromide (0.847 g, 2.63 mmol) at 25 °C, 3-methyl-2-methylenebutanenitrile (7.50 g, 79 mmol) was added over 20 min. The reaction mixture was stirred at 25 °C for 15 h. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (40 mL). The combined organic layers were washed successively with water and brine. The volatiles were removed under reduced pressure, and the resulting residue was distilled on a Kugelrohr under reduced pressure (2 mbar and 130 °C) to give 3-methyl-2-(((2-methylenehexyl)oxy)methyl)butanenitrile (1.5 g, 13.6%) as a colorless liquid. GC purity 99.0%. Scent note: ND.

[0176] 1 H NMR(300MHz,CDCl3):δ 5.00(s,1H),4.92(s,1H),3.95(s,2H),3.49-3.60(m,2H),2.67-2.74(m,1H),2. 00-2.07(m,3H),1.25-1.46(m,4H),1.08(d,J=6.9Hz,6H),0.93(t,J=6.7Hz,3H).

[0177] Example 39 Synthesis of 2-((3-methyl-2-methylenebutoxy)methyl)pentanenitrile To a mixture of 3-methyl-2-methylenebutan-1-ol (10.0 g, 100 mmol), KOH (6.16 g, 110 mmol), water (10 mL), and tetrabutylammonium bromide (1.60 g, 4.99 mmol) at 25 °C, 2-methylenepentanenitrile (14.25 g, 150 mmol) was added over 20 min. The reaction mixture was stirred at 25 °C for 15 h. The reaction mixture was acidified to pH 3-4 with dilute HCl. The organic layer was separated, and the aqueous layer was extracted with diethyl ether (60 mL). The combined organic layers were washed successively with water and brine. The volatiles were removed under reduced pressure, and the resulting residue was distilled under reduced pressure (2 mbar and 103 °C) to give 2-((3-methyl-2-methylenebutoxy)methyl)pentanenitrile (3.0 g, 15.36 mmol, 15.39%) as a colorless liquid. GC purity 98.0%. Scent note: ND.

[0178] 1 H NMR(300MHz,CDCl3):δ 4.99(s,1H),4.94(s,1H),4.01(s,2H),3.47-3.57(m,2H),2.75-2.82(m,1H),2. 29-2.38(m,1H),1.44-1.68(m,5H),1.06(d,J=6.9Hz,6H),0.94(t,J=5.4Hz,3H).

[0179] Example 40 Synthesis of 3-((5-methylenenon-1-en-4-yl)oxy)propanenitrile: Step 1: Synthesis of 5-methylenenon-1-en-4-ol To a solution of 2-methylenehexanal (50.0 g, 446 mmol) in tetrahydrofuran (350 mL) cooled to 0 °C, allylmagnesium chloride (267 mL, 535 mmol, 2 M solution in THF) was added over 15 min. The reaction mixture was stirred at room temperature for 3 h. The reaction mixture was then diluted with saturated ammonium chloride solution (50 mL), and the mixture was extracted with ethyl acetate (3 × 100 mL). The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The crude product was purified by column chromatography using 100-200 silica gel and 3% ethyl acetate in hexane as the eluent to give 5-methylenenon-1-en-4-ol (26.0 g, 169 mmol, 37.8%) as a colorless liquid.

[0180] 1 H NMR(300MHz,CDCl3):δ 5.72 5.86(m,1H),5.09-5.16(m,2H),5.03(s,1H),4.85(d,J=1.2Hz,1H),4.08-4.12(m,1H),2.34-2.38( m,1H),2.21-2.31(m,1H),1.92-2.13(m,2H),1.80(s,1H),1.24-1.50(m,4H),0.90(t,J=7.2Hz,3H).

[0181] Step 2: Synthesis of 3-((5-methylenenon-1-en-4-yl)oxy)propanenitrile: A solution of 5-methylenenon-1-en-4-ol (10.0 g, 64.8 mmol), potassium hydroxide (4.00 g, 71.3 mmol), and tetrabutylammonium bromide (1.04 g, 3.24 mmol) in water (15 mL) was stirred at room temperature for 30 minutes. Then, acrylonitrile (4.13 g, 78 mmol) was slowly added to the mixture, and the reaction was continued at room temperature for 16 hours.

[0182] The reaction mixture was acidified with dilute HCl to pH 3 to 4. The organic layer was separated, washed with water (20 ml), dried over anhydrous sodium sulfate, and concentrated.

[0183] The residue was purified by column chromatography on silica gel with a size of 100 mesh to 200 mesh using 3% to 4% ethyl acetate in hexane as an eluent to obtain a mixture, which was distilled under reduced pressure (150°C and 3 mbar) to obtain 3-((5-methylenenon-1-en-4-yl)oxy)propanenitrile (2.6 g, 12.54 mmol, 19.35%) as a colorless liquid. Odor note: Dry, nitrile-like, gentle.

[0184] 1 H NMR(300MHz,CDCl3):δ 5.74-5.80(m,1H),4.96-5.10(m,4H),3.59-3.75(m,2H),3.40-3.47(m,1H),2.56(t,J=6. 3Hz, 2H), 2.24-2.38 (m, 2H), 1.94-2.01 (m, 2H), 1,32-1.45 (m, 4H), 0.92 (t, J=7.2Hz, 3H).

[0185] Example 41 Synthesis of 3-((5-methylenenon-1-en-4-yl)oxy)butanenitrile A solution of 5-methylenenon-1-en-4-ol (10.0 g, 64.8 mmol), potassium hydroxide (4.00 g, 71.3 mmol), and tetrabutylammonium bromide (1.04 g, 3.24 mmol) in water (15 mL) was stirred at room temperature for 30 minutes. Next, crotononitrile (cis + trans) (6.36 mL, 78 mmol) was slowly added to the mixture, and the reaction was continued at room temperature for 16 hours. The reaction mixture was acidified with dilute HCl to a pH of 3-4. The organic layer was separated, washed with water (20 mL), dried over anhydrous sodium sulfate, and concentrated. The residue was purified by column chromatography on silica gel with a size of 100 mesh to 200 mesh using 3% to 4% ethyl acetate in hexane as the eluent to give a mixture which was further distilled by distillation under reduced pressure (150°C and 3 mbar) to give 3-((5-methylenenon-1-en-4-yl)oxy)butanenitrile (4.2 g, 18.97 mmol, 29.3%) as a colorless liquid. Scent note: ND.

[0186] 1 H NMR(300MHz,CDCl3):δ 5.75-5.80(m,1H),4.93-5.10(m,4H),3.68-3.81(m,2H),2.45(d,J=5.7Hz,2H), 2.24-2.38(m,2H),1.94-2.02(m,2H),1.23-1.48(m,7H),0.92(t,J=6.9Hz,3H).

[0187] Example of composition evaluation In the following invention, Example (A) containing the compound from Example 13 (3-((2-methylenehexyl)oxy)propanenitrile) and Comparative Example B containing the commercially available compound methyl nonyl ketone illustrate a compositional evaluation study in a woody accord fragrance used in shampoo (C=blank, IPM=isopropyl myristate).

[0188] [Table 2]

[0189] The incorporation of 5.5% (w / w) 3-((2-methylenehexyl)oxy)propanenitrile (10% (w / w)) in IPM resulted in a very diffused and powerful woody note. Furthermore, its incorporation also imparted a very nice floral character to the overall accord. On the other hand, when 10% (w / w) methyl nonyl ketone in IPM was used in the above accord, only a poor woody note was observed.

[0190] In the following invention, Example (A) containing the compound from Example 13 (3-((2-methylenehexyl)oxy)propanenitrile) and Comparative Example B containing the commercial compound methyl nonyl ketone illustrate a compositional evaluation study in the fragrance of a fougere accord used in a shampoo (C = blank, IPM = isopropyl myristate).

[0191] [Table 3]

[0192] The incorporation of 14.1% (w / w) 3-((2-methylenehexyl)oxy)propanenitrile (10% (w / w)) in the IPM provided excellent enhanced fougere properties. Furthermore, its incorporation also imparted increased strength to the overall accord. On the other hand, when 10% (w / w) methyl nonyl ketone in the IPM was used in the above accord, only insufficient fougere effect was observed.

[0193] In the following invention, Example (A) containing the compound from Example 13 (3-((2-methylenehexyl)oxy)propanenitrile) and Comparative Example B containing the commercial compound methyl nonyl ketone illustrate a compositional evaluation study in the fragrance of a citrus accord used in fabric softeners (C=blank, IPM=isopropyl myristate).

[0194] [Table 4]

[0195] The incorporation of 0.9% (w / w) 3-((2-methylenehexyl)oxy)propanenitrile (10% (w / w)) in the IPM provided a wonderful citrus freshness enhancement. Furthermore, its incorporation also provided increased intensity to the overall accord, as well as a more organg, juicy, and sparkling character. On the other hand, when 10% (w / w) methyl nonyl ketone in the IPM was used in the above accord, only a weak citrus effect was observed.

[0196] In the following invention, Example (A) containing the compound from Example 13 (3-((2-methylenehexyl)oxy)propanenitrile) and Comparative Example B containing the commercial compound methyl nonyl ketone illustrate a compositional evaluation study in a rose accord fragrance used in fabric softeners (C=blank, IPM=isopropyl myristate).

[0197] [Table 5]

[0198] The incorporation of 10% (w / w) 3-((2-methylenehexyl)oxy)propanenitrile (10% (w / w)) in the IPM gave enhanced floral and rosy properties. Furthermore, its incorporation also imparted a sweet chocolate note with increased intensity to the overall accord. On the other hand, when 10% (w / w) methyl nonyl ketone in the IPM was used in the above accord, only a weak rosy effect was observed.

Claims

1. Formula (I) 【Chemical 1】 (In the formula, R 1 is a hydrogen atom or a methyl group, and R 2 is a hydrogen atom or an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms, R 3 is either an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms, and R 4 is a hydrogen atom or a methyl group, or an alkyl group having up to 9 carbon atoms or an alkenyl group containing up to 9 carbon atoms, provided that: Excluding compounds in which R 3 is a methyl group, R 2 is a hydrogen atom, R 4 is a hydrogen atom, and R 1 is a hydrogen atom. Excluding compounds in which R 3 is a methyl group, R 2 is a hydrogen atom, R 4 is a hydrogen atom, and R 1 is a methyl group. - Compounds of the formula (excluding compounds in which R 3 is a methyl group, R 2 is a hydrogen atom, R 4 is a methyl group, and R 1 is a hydrogen atom).

2. R 4 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or 9-octenyl.

3. R 2 3. A compound of formula (I) according to claim 1 or 2, wherein is a hydrogen atom or an alkyl or alkenyl group having up to 5 carbon atoms.

4. R 2 The compound of formula (I) according to claim 3, wherein is methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, or n-pentyl.

5. R 3 is methyl, ethyl, n-propyl, i-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or 9-octenyl.

6. 1) 3-(3-methyl-2-methylenebutoxy)propanenitrile 2) 3-((5-methyl-4-methylenehexan-3-yl)oxy)butanenitrile 3) 3-(2-methylenebutoxy)propanenitrile 4) 3-(2-methylenebutoxy)butanenitrile 5) 3-((3-methylenepentan-2-yl)oxy)propanenitrile 6) 3-((3-methylenepentan-2-yl)oxy)butanenitrile 7) 3-((4-methylenehexan-3-yl)oxy)propanenitrile 8) 3-((4-methylenehexan-3-yl)oxy)butanenitrile 9) 3-((2-methylenepentyl)oxy)propanenitrile 10) 3-((3-methylenehexan-2-yl)oxy)propanenitrile 11) 3-((3-methylenehexan-2-yl)oxy)butanenitrile 12) 3-((4-methyleneheptan-3-yl)oxy)propanenitrile 13) 3-((2-methylenehexyl)oxy)propanenitrile 14) 3-((2-methylenehexyl)oxy)butanenitrile 15) 3-((4-methyleneoctan-3-yl)oxy)propanenitrile 16) 3-((4-methyleneoctan-3-yl)oxy)butanenitrile 17) 3-((2-methyleneheptyl)oxy)propanenitrile 18) 3-((2-methyleneheptyl)oxy)butanenitrile 19) 3-((3-methyleneoctan-2-yl)oxy)propanenitrile 20) 3-((3-methyleneoctan-2-yl)oxy)butanenitrile 21) 3-((4-methylenenonan-3-yl)oxy)propanenitrile 22) 3-((4-methylenenonan-3-yl)oxy)butanenitrile 23) 3-((2-methyleneoctyl)oxy)butanenitrile 24) 3-((3-methylenenonan-2-yl)oxy)propanenitrile 25) 3-((4-methylenedecan-3-yl)oxy)propanenitrile 26) 3-((4-methylenedecan-3-yl)oxy)butanenitrile 27) 3-((2-methylenenonyl)oxy)propanenitrile 28) 3-((3-methylenedecan-2-yl)oxy)propanenitrile 29) 3-((3-methylenedecan-2-yl)oxy)butanenitrile 30) 3-((2-methylenedec-9-en-1-yl)oxy)propanenitrile 31) 3-((2-methylenedec-9-en-1-yl)oxy)butanenitrile 32) 3-((2-methyl-5-methylenenonan-4-yl)oxy)propanenitrile 33) 3-((2-methyl-5-methylenenonan-4-yl)oxy)butanenitrile 34) 3-((6-methylenedecan-5-yl)oxy)propanenitrile 35) 3-((6-methylenedecan-5-yl)oxy)butanenitrile 36) 2-(((2-methylenehexyl)oxy)methyl)hexanenitrile 37) 2-(((2-methylenehexyl)oxy)methyl)pentanenitrile 38) 3-methyl-2-(((2-methylenehexyl)oxy)methyl)butanenitrile 39) 2-((3-methyl-2-methylenebutoxy)methyl)pentanenitrile 40) 3-((5-methylenenon-1-en-4-yl)oxy)propanenitrile 41) 3-((5-methylenenon-1-en-4-yl)oxy)butanenitrile 42) 2-(((2-methylenehexyl)oxy)methyl)butanenitrile 2. The compound of formula (I) according to claim 1, selected from:

7. The compound of formula (I) according to claim 1, which is a 3-(2-methylenealkoxy)alkanenitrile.

8. A fragrance, flavor, and / or deodorizing / masking composition comprising a compound of formula (I) according to any one of claims 1 to 7.

9. 9. The fragrance, flavor, and / or deodorizing / masking composition according to claim 8, wherein the content of the compound of formula (I) is at least 0.1% by weight.

10. 10. The fragrance, flavor, and / or deodorizing / masking composition according to claim 9, wherein the content of the compound of formula (I) is at least 1% by weight.

11. The fragrance, flavor, and / or deodorizing / masking composition according to any one of claims 8 to 10, wherein the content of the compound of formula (I) is less than 50% by weight.

12. 12. The fragrance, flavor, and / or deodorizing / masking composition according to claim 11, wherein the content of the compound of formula (I) is less than 25% by weight.

13. Use of a fragrance, flavor and / or deodorizing / masking composition according to any one of claims 8 to 12 in a perfumed or flavored product.

14. Use of a compound of formula (I) according to any one of claims 1 to 7 in perfumed or flavoured products.

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