Perfume composition

Abstract

The present invention is a perfume composition that contains a 3-(4-alkylphenyl)propanenitrile represented by general formula (1) as an active ingredient. The perfume composition contains a 3-(4-alkylphenyl)propanenitrile that has a floral aroma and a verdant aroma or a fruity aroma as an active ingredient and has a strong floral aroma. The present invention is also a method for using a 3-(4-alkylphenyl)propanenitrile as a perfume and a production method for a 3-(4-alkylphenyl)propanenitrile. (In formula (1), R represents a C2–4 alkyl group.)

Description

fragrance composition

[0001] The present invention relates to a fragrance composition.

[0002] Nitrile compounds having a phenyl group are known as fragrance ingredients, such as paeonyl (2-cyclohexylidene-2-phenylacetonitrile), which has a grapefruit, geranium, and rose floral scent, and cinnamyl nitrile, which has a cinnamon and cassia scent (Non-Patent Document 1). Some nitriles corresponding to aldehydes used in fragrances are known to have similar fragrance notes. Non-Patent Document 2 describes a method for deriving the corresponding nitriles from aldehydes used in fragrances, and describes that the derived nitriles are useful as fragrance ingredients.

[0003] Edited by the Synthetic Fragrance Editorial Committee, "New and Expanded Edition: Synthetic Fragrance: Chemistry and Product Knowledge," 2016, pp. 725-726; Flavor Fragrance Journal, 2020, vol. 35, pp. 425-435, published by The Chemical Daily.

[0004] As mentioned above, some nitrile compounds are used as fragrances, but new fragrances are needed to enhance the value of products such as fragrances, cosmetics, detergents, hygiene products, miscellaneous goods, pharmaceuticals, and foods. Typically, fragrances are used as blended fragrances, consisting of a mixture of multiple fragrances, and there is a demand for fragrance components that exhibit excellent effects, particularly when mixed with other fragrances. Therefore, an object of the present invention is to provide a fragrance composition having novel fragrances and properties, a use of a compound that can impart novel fragrances and properties to a fragrance composition, and a method for imparting fragrance.

[0005] The present inventors have discovered that a fragrance composition containing a specific nitrile compound as an active ingredient has novel fragrances and properties, that the nitrile compound can be used as a fragrance, and that the nitrile compound can impart a fragrance useful as a fragrance, and have thus completed the present invention.

[0006] That is, the present invention is as follows: [1] A fragrance composition containing, as an active ingredient, 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1): (In formula (1), R represents an alkyl group having 2 to 4 carbon atoms.) [2] The fragrance composition according to the above item [1], further containing a fragrance substance other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1). [3] The fragrance composition according to the above item [2], wherein the fragrance substance other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1) is at least one selected from the group consisting of hydrocarbons, alcohols, esters, phenols, aldehydes, ketones, acetals, ketals, ethers, natural essential oils, natural extracts, and nitriles other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1). [4] The fragrance composition according to any one of the above items [1] to [3], wherein R is at least one selected from the group consisting of an ethyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a tertiary butyl group. [5] The fragrance composition according to any one of [1] to [4] above, wherein R is at least one selected from the group consisting of an isopropyl group, a normal butyl group, and an isobutyl group. [6] The fragrance composition according to any one of [1] to [5] above, wherein R is a normal butyl group. [7] The fragrance composition according to any one of [1] to [6] above, wherein 3-(2-alkylphenyl)propanenitrile represented by the following general formula (2) is contained in an amount of 0.03 to 0.8% by mass relative to the 3-(4-alkylphenyl)propanenitrile represented by formula (1): (In formula (2), R represents an alkyl group having 2 to 4 carbon atoms.) [8] Use of 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1) as a fragrance. (In formula (1), R represents an alkyl group having 2 to 4 carbon atoms.) [9] The use according to the above item [8], wherein R is at least one selected from the group consisting of an ethyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group.

[10] The use according to the above item [8] or [9], wherein the 3-(4-alkylphenyl)propanenitrile represented by formula (1) imparts a floral scent, a green scent, or a fruity scent.

[11] The use according to any one of the above items [8] to

[10] , wherein R is at least one selected from the group consisting of an isopropyl group and an isobutyl group.

[12] The use according to the above item

[11] , wherein the 3-(4-alkylphenyl)propanenitrile represented by formula (1) imparts a floral scent, a green scent, and a fruity scent.

[13] The use according to any one of the above items [8] to

[10] , wherein R is a normal butyl group.

[14] The use according to the above

[13] , wherein the 3-(4-alkylphenyl)propanenitrile represented by the formula (1) imparts a floral fragrance, a fruity fragrance, and a spicy fragrance.

[15] A fragrance-imparting method, wherein a 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1) imparts a floral fragrance, a green fragrance, or a fruity fragrance. (In formula (1), R represents an alkyl group having 2 to 4 carbon atoms.)

[16] A method for producing 3-(4-alkylphenyl)propanenitrile, the method comprising the steps of: a step of converting 4-alkylbenzaldehyde represented by formula (3) below, which is used as a raw material, into cinnamonitrile represented by formula (4) below by a condensation reaction with acetonitrile; and a hydrogenation step, in this order. (In formulas (3) and (4), R represents an alkyl group having 2 to 4 carbon atoms.)

[17] A nitrile composition containing 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1) and 3-(2-alkylphenyl)propanenitrile represented by the following general formula (2), wherein the 3-(2-alkylphenyl)propanenitrile represented by the following general formula (2) is contained in an amount of 0.03 to 0.8 mass % relative to the 3-(4-alkylphenyl)propanenitrile represented by formula (1). (In formula (1), R represents an alkyl group having 2 to 4 carbon atoms. In formula (2), R represents an alkyl group having 2 to 4 carbon atoms.)

[0007] According to the present invention, a fragrance composition having a strong floral fragrance can be provided by containing, as an active ingredient, 3-(4-alkylphenyl)propanenitrile, which can impart a floral fragrance and a green or fruity fragrance.Furthermore, the present invention can provide use of 3-(4-alkylphenyl)propanenitrile having a floral fragrance and a green or fruity fragrance as a fragrance, a fragrance imparting method, and a method for producing 3-(4-alkylphenyl)propanenitrile.

[0008] Hereinafter, in this specification, the expression "XX to YY" means "XX or more and YY or less."

[0009] [Fragrance Composition] The fragrance composition of the present invention is a fragrance composition containing 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1) as an active ingredient. (In formula (1), R represents an alkyl group having 2 to 4 carbon atoms.)

[0010] The fragrance composition of the present invention contains, as an active ingredient, 3-(4-alkylphenyl)propanenitrile, which has a floral fragrance and a green or fruity fragrance, and therefore has a strong floral fragrance and excellent fragrance strength, making it useful as a fragrance component for various products.

[0011] <3-(4-Alkylphenyl)propanenitrile> In formula (1), R represents an alkyl group having 2 to 4 carbon atoms. Specifically, R is preferably at least one selected from the group consisting of an ethyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group, more preferably at least one selected from the group consisting of an isopropyl group, a normal butyl group, and an isobutyl group, and even more preferably a normal butyl group. When R is at least one selected from the group consisting of an ethyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group, the compound has a green or fruity scent in addition to a floral scent, and can impart a strong floral scent, making it extremely useful as an active ingredient in a fragrance composition. When R is at least one selected from the group consisting of an isopropyl group and an isobutyl group, the compound has a green and fruity scent in addition to a floral scent, and can impart a strong floral scent, making it extremely useful as an active ingredient in a fragrance composition. When R is a normal butyl group, the compound has a floral scent, as well as fruity and spicy scents, and can impart a strong floral scent, making it very useful as an active ingredient in a fragrance composition. Furthermore, when R is a normal butyl group, the fragrance intensity and diffusibility of the fragrance composition can be significantly improved.

[0012] The 3-(4-alkylphenyl)propanenitrile represented by the above formula (1) is useful as an active ingredient in fragrance compositions, and has a floral odor and a green or fruity odor, can impart a strong floral odor, and can further impart fragrance strength and diffusibility. When R is an ethyl group, in particular, the compound has a green odor in addition to the floral odor, imparting a strong floral odor. When R is an isopropyl group, in particular, the compound has a green and fruity odor in addition to the floral odor, imparting a strong floral odor. When R is a normal butyl group, in particular, the compound has a fruity and spicy odor in addition to the floral odor, imparting a strong floral odor. Furthermore, the fragrance strength and diffusibility of the fragrance composition can be significantly improved. When R is an isobutyl group, in particular, the compound has a green and fruity odor in addition to the floral odor, imparting a strong floral odor. When R is a tertiary butyl group, in particular, the compound has a green odor in addition to the floral odor, imparting a strong floral odor.

[0013] The fragrance composition of the present invention preferably contains a 3-(2-alkylphenyl)propanenitrile represented by the following general formula (2). The fragrance composition of the present invention more preferably contains 0.03 to 0.8% by mass of the 3-(2-alkylphenyl)propanenitrile represented by formula (2) relative to the 3-(4-alkylphenyl)propanenitrile represented by formula (1). It is believed that the inclusion of a small amount of the 3-(2-alkylphenyl)propanenitrile represented by formula (2) results in a more complex and pleasant fragrance note. (In formula (2), R represents an alkyl group having 2 to 4 carbon atoms.)

[0014] R in formula (2) is an alkyl group having 2 to 4 carbon atoms, and is preferably the same as the 3-(4-alkylphenyl)propanenitrile represented by formula (1) contained in the fragrance composition. That is, when 3-(4-n-butylphenyl)propanenitrile is contained as an active ingredient in the fragrance composition, it is preferable that 3-(2-n-butylphenyl)propanenitrile is also contained.

[0015] The content of the 3-(4-alkylphenyl)propanenitrile in the fragrance composition of the present invention may be appropriately adjusted depending on the type of fragrance composition, the type and intensity of the desired fragrance, and the like, and is preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass, even more preferably 0.5 to 30% by mass, still more preferably 1.0 to 20% by mass, and even more preferably 1.5 to 10% by mass.

[0016] <Other Ingredients and Products in Which the 3-(4-alkylphenyl)propanenitrile can be used> Examples of other ingredients besides the 3-(4-alkylphenyl)propanenitrile contained in the fragrance composition containing the 3-(4-alkylphenyl)propanenitrile include fragrance substances other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1), surfactants, solvents, antioxidants, and colorants, and at least one selected from the group consisting of fragrance substances other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1), surfactants, solvents, antioxidants, and colorants is preferred, at least one selected from the group consisting of fragrance substances other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1) and solvents is more preferred, and a fragrance substance other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1) is even more preferred. That is, a preferred fragrance composition of the present invention contains the 3-(4-alkylphenyl)propanenitrile represented by formula (1) as an active ingredient and contains a fragrance substance other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1). By adding a fragrance substance other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1), the scent can be adjusted to suit the target product. Furthermore, by adding a solvent, it becomes easy to dissolve and impregnate the target product, and the strength and persistence of the scent can be adjusted.

[0017] The fragrance substance other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1) is not particularly limited as long as it is a conventionally known fragrance component, and a wide range of fragrances can be used. For example, the following can be selected and used alone or in any mixture of two or more kinds in any ratio:

[0018] The fragrance substance other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1) is preferably at least one selected from the group consisting of hydrocarbons, alcohols, esters, phenols, aldehydes, ketones, acetals, ketals, ethers, natural essential oils, natural extracts, and nitriles other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1). Among these, the fragrance substance is more preferably at least one selected from the group consisting of hydrocarbons, alcohols, esters, phenols, aldehydes, ketones, acetals, ketals, and ethers, even more preferably at least one selected from the group consisting of alcohols, esters, phenols, and aldehydes, even more preferably at least one selected from the group consisting of esters and aldehydes, and even more preferably esters. Combining the 3-(4-alkylphenyl)propanenitrile with such a fragrance substance is preferred because it can produce a stronger floral scent.

[0019] Examples of hydrocarbons include limonene, α-pinene, β-pinene, terpinene, cedrene, longifolene, and valencene.

[0020] Examples of alcohols include linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenol, ethyl linalool, farnesol, nerolidol, cis-3-hexenol, cedrol, menthol, borneol, β-phenylethyl alcohol, benzyl alcohol, phenylhexanol, 2,2,6-trimethylcyclohexyl-3-hexanol, 1-(2-t-butylcyclohexyloxy)-2-butanol, 4-isopropylcyclohexyl hexanemethanol, 4-t-butylcyclohexanol, 4-methyl-2-(2-methylpropyl)tetrahydro-2H-pyran-4-ol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, isocamphylcyclohexanol, and 3,7-dimethyl-7-methoxyoctan-2-ol.

[0021] Examples of phenols include eugenol, thymol, and vanillin.

[0022] Examples of esters include linalyl formate, citronellyl formate, geranyl formate, n-hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, terpinyl acetate, nopyr acetate, bornyl acetate, isobornyl acetate, o-t-butylcyclohexyl acetate, p-t-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styrallyl acetate, cinnamyl acetate, dimethylbenzylcarbinyl acetate, 3-pentyltetrahydropyran-4-yl acetate, citronellyl propionate, tricyclodecenylpropionate, onate, allyl cyclohexylpropionate, ethyl 2-cyclohexylpropionate, benzyl propionate, citronellyl butyrate, dimethylbenzylcarbinyl n-butyrate, tricyclodecenyl isobutyrate, methyl 2-nonenoate, methyl benzoate, benzyl benzoate, methyl cinnamate, methyl salicylate, n-hexyl salicylate, cis-3-hexenyl salicylate, geranyl tiglate, cis-3-hexenyl tiglate, methyl jasmonate, methyl dihydrojasmonate, methyl-2,4-dihydroxy-3,6-dimethylbenzoate, ethyl methylphenylglycidate, methyl anthranilate, fultate, etc. Among these, at least one selected from the group consisting of linalyl acetate, benzyl acetate, and cinnamyl acetate is preferred, and benzyl acetate is more preferred.

[0023] Examples of aldehydes include n-octanal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecenal, citronellal, citral, hydroxycitronellal, dimethyltetrahydrobenzaldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, 2-cyclohexylpropanal, p-t-butyl-α-methylhydrocinnamic aldehyde, p-t-butylhydrocinnamic aldehyde, p-isopropyl-α-methylhydrocinnamic aldehyde, p-ethyl-α,α-dimethylhydrocinnamic aldehyde, α-amylcinnamic aldehyde, α-hexylcinnamic aldehyde, piperonal, and α-methyl-3,4-methylenedioxyhydrocinnamic aldehyde.

[0024] Examples of ketones include methylheptenone, 4-methylene-3,5,6,6-tetramethyl-2-heptanone, amylcyclopentanone, 3-methyl-2-(cis-2-penten-1-yl)-2-cyclopenten-1-one, methylcyclopentenolone, rose ketone, γ-methylionone, α-ionone, carvone, menthone, camphor, nootkatone, benzylacetone, anisylacetone, methyl β-naphthyl ketone, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, maltol, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, muscone, civetone, cyclopentadecanone, and cyclohexadecenone.

[0025] Examples of acetals and ketals include acetaldehyde ethyl phenylpropyl acetal, citral diethyl acetal, phenylacetaldehyde glycerin acetal, and ethyl acetoacetate ethylene glycol ketal.

[0026] Examples of ethers include anethole, β-naphthyl methyl ether, β-naphthyl ethyl ether, limonene oxide, rose oxide, 1,8-cineole, racemic or optically active dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan, and the like.

[0027] Examples of lactones include γ-nonalactone, γ-undecalactone, σ-decalactone, γ-jasmolactone, coumarin, cyclopentadecanolide, cyclohexadecanolide, ambrettolide, ethylene brassylate, and 11-oxahexadecanolide.

[0028] Examples of natural essential oils and extracts include orange, lemon, bergamot, mandarin, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, geranium, jasmine, ylang-ylang, anise, clove, ginger, nutmeg, cardamom, cedar, cypress, sandalwood, vetiver, patchouli, and labdanum.

[0029] Examples of nitriles other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1) include citronellyl nitrile.

[0030] Examples of the solvent include dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, triethyl citrate, etc. Examples of the surfactant include polyoxyethylene lauryl sulfate ether, etc.

[0031] The fragrance composition containing the 3-(4-alkylphenyl)propanenitrile represented by the general formula (1) can be used as a fragrance component in various products. Examples of products in which the fragrance composition can be used include fragrance products such as perfumes and colognes; hair cosmetics such as shampoos, conditioners, hair tonics, hair creams, mousses, gels, pomades, sprays, and other hair cosmetics; skin cosmetics such as lotions, serums, creams, emulsions, packs, foundations, face powders, lipsticks, and various types of makeup; dishwashing detergents, laundry detergents, softeners, disinfectant detergents, deodorizing detergents, room air fresheners, furniture care products, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, bactericides, repellents, and other various health and hygiene detergents; quasi-drugs such as toothpaste, mouthwash, bath additives, antiperspirant products, and perm solution; miscellaneous goods such as toilet paper and tissue paper; pharmaceuticals; and foods.

[0032] The amount of the fragrance composition in the product is not particularly limited, and can be selected depending on the type, properties, and sensory effects of the product to be scented. For example, the amount of the fragrance composition in the product is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.001% by mass or more. It is also preferably 80% by mass or less, even more preferably 60% by mass or less, and even more preferably 40% by mass or less. When the fragrance composition is used as an aroma oil, perfume, or the like, the amount of the fragrance composition in the product may be 80% by mass or more, or even 100% by mass.

[0033] [Nitrile Composition] The nitrile composition of the present invention contains a 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1) and a 3-(2-alkylphenyl)propanenitrile represented by the following general formula (2), and is a nitrile composition containing 0.03 to 0.8 mass % of the 3-(2-alkylphenyl)propanenitrile represented by the following general formula (2) relative to the 3-(4-alkylphenyl)propanenitrile represented by formula (1): (In formula (1), R represents an alkyl group having 2 to 4 carbon atoms. In formula (2), R represents an alkyl group having 2 to 4 carbon atoms.)

[0034] The nitrile composition of the present invention contains, as an active ingredient, 3-(4-alkylphenyl)propanenitrile having a floral odor and a green or fruity odor. The inclusion of a small amount of 3-(2-alkylphenyl)propanenitrile represented by formula (2) is thought to result in a more complex and pleasant odor tone, and the composition has a strong floral odor and excellent odor strength. Therefore, the composition is useful as a fragrance component for various products. The composition is also useful as a raw material for fragrance compositions.

[0035] <3-(4-Alkylphenyl)propanenitrile> In formula (1), R represents an alkyl group having 2 to 4 carbon atoms. Specifically, R is preferably at least one selected from the group consisting of an ethyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group, more preferably at least one selected from the group consisting of an isopropyl group, a normal butyl group, and an isobutyl group, and even more preferably a normal butyl group. When R is at least one selected from the group consisting of an ethyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group, the compound has a green or fruity scent in addition to a floral scent, and can impart a strong floral scent, making it extremely useful as an active ingredient in a fragrance composition. When R is at least one selected from the group consisting of an isopropyl group and an isobutyl group, the compound has a green and fruity scent in addition to a floral scent, and can impart a strong floral scent, making it extremely useful as an active ingredient in a fragrance composition. When R is a normal butyl group, the compound has a floral scent, as well as fruity and spicy scents, and can impart a strong floral scent, making it very useful as an active ingredient in a fragrance composition. Furthermore, when R is a normal butyl group, the fragrance intensity and diffusibility of the fragrance composition can be significantly improved.

[0036] The 3-(4-alkylphenyl)propanenitrile represented by the above formula (1) is useful as an active ingredient in fragrance compositions, and has a floral odor and a green or fruity odor, can impart a strong floral odor, and can further impart fragrance strength and diffusibility. When R is an ethyl group, in particular, the compound has a green odor in addition to the floral odor, imparting a strong floral odor. When R is an isopropyl group, in particular, the compound has a green and fruity odor in addition to the floral odor, imparting a strong floral odor. When R is a normal butyl group, in particular, the compound has a fruity and spicy odor in addition to the floral odor, imparting a strong floral odor. Furthermore, the fragrance strength and diffusibility of the fragrance composition can be significantly improved. When R is an isobutyl group, in particular, the compound has a green and fruity odor in addition to the floral odor, imparting a strong floral odor. When R is a tertiary butyl group, in particular, the compound has a green odor in addition to the floral odor, imparting a strong floral odor.

[0037] <3-(2-Alkylphenyl)propanenitrile> In formula (2), R represents an alkyl group having 2 to 4 carbon atoms. When 3-(2-alkylphenyl)propanenitrile is contained in the nitrile composition of the present invention, R in formula (2) is preferably the same as the 3-(4-alkylphenyl)propanenitrile contained in the nitrile composition, and is the same as R in formula (1). Specifically, R is preferably at least one selected from the group consisting of an ethyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group, more preferably at least one selected from the group consisting of an isopropyl group, a normal butyl group, and an isobutyl group, and even more preferably a normal butyl group. When R is at least one selected from the group consisting of an ethyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group, the compound has a green or fruity scent in addition to a floral scent, and can impart a strong floral scent, making it extremely useful as an active ingredient in a fragrance composition. When R is at least one selected from the group consisting of an isopropyl group and an isobutyl group, the compound has a floral scent, a green scent, and a fruity scent in addition to a floral scent, and can impart a strong floral scent, making it extremely useful as an active ingredient in a fragrance composition. When R is a normal butyl group, the compound has a floral scent, a fruity scent, and a spicy scent in addition to a floral scent, and can impart a strong floral scent, making it extremely useful as an active ingredient in a fragrance composition. Furthermore, when R is a normal butyl group, the fragrance intensity and diffusibility of the fragrance composition can be further significantly improved.

[0038] The nitrile compound of the present invention contains the 3-(2-alkylphenyl)propanenitrile represented by formula (2) in an amount of preferably 0.03 to 0.8% by mass, more preferably 0.04 to 0.7% by mass, and even more preferably 0.2 to 0.7% by mass, based on the 3-(4-alkylphenyl)propanenitrile represented by formula (1).

[0039] When the nitrile composition of the present invention is contained in a fragrance composition, the content of the nitrile composition in the fragrance composition may be appropriately adjusted depending on the type of fragrance composition, the type and intensity of the desired fragrance, etc., and is preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass, even more preferably 0.5 to 30% by mass, still more preferably 1.0 to 20% by mass, and still more preferably 1.5 to 10% by mass.

[0040] [Use as a fragrance] 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1) has a floral scent and a green or fruity scent, and therefore can be used as a fragrance. The use of 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1) as a fragrance is also included in the present invention. (In formula (1), R represents an alkyl group having 2 to 4 carbon atoms.)

[0041] In formula (1), R represents an alkyl group having 2 to 4 carbon atoms. Specifically, R is preferably at least one selected from the group consisting of an ethyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group, more preferably at least one selected from the group consisting of an isopropyl group, a normal butyl group, and an isobutyl group, and even more preferably a normal butyl group. When R is at least one selected from the group consisting of an ethyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group, the compound has a green or fruity scent in addition to a floral scent, and is therefore more suitable for use as a fragrance. When R is at least one selected from the group consisting of an isopropyl group and an isobutyl group, the compound has a green and fruity scent in addition to a floral scent, and is therefore even more suitable for use as a fragrance. When R is a normal butyl group, the compound has a fruity and spicy scent in addition to a floral scent, and is therefore even more suitable for use as a fragrance.

[0042] When R is an ethyl group, in particular, the fragrance has a green scent in addition to a floral scent. When R is an isopropyl group, in particular, the fragrance has a green and fruity scent in addition to a floral scent. When R is an n-butyl group, in particular, the fragrance has a fruity and spicy scent in addition to a floral scent. When R is an isobutyl group, in particular, the fragrance has a green and fruity scent in addition to a floral scent. When R is a tertiary butyl group, in particular, the fragrance has a green scent in addition to a floral scent.

[0043] The 3-(4-alkylphenyl)propanenitrile represented by the above formula (1) has a floral scent and a green or fruity scent. Therefore, the use of the 3-(4-alkylphenyl)propanenitrile represented by the formula (1) imparts a floral scent, a green or fruity scent to a product. Furthermore, the strength and diffusibility of the scent contained in the product can be improved. When R is an ethyl group, a green scent is imparted in addition to the floral scent. When R is an isopropyl group, a green and fruity scent is imparted in addition to the floral scent. When R is a n-butyl group, a fruity and spicy scent is imparted in addition to the floral scent. Furthermore, the strength and diffusibility of the scent contained in the product can be significantly improved. When R is an isobutyl group, a green and fruity scent is imparted in addition to the floral scent. When R is a tertiary butyl group, a green scent is imparted in addition to the floral scent.

[0044] The 3-(4-alkylphenyl)propanenitrile represented by formula (1) can be used as a fragrance component for various products. When the 3-(4-alkylphenyl)propanenitrile represented by formula (1) is used as a fragrance component for various products, it may be used as one component of the fragrance composition. Examples of products in which the 3-(4-alkylphenyl)propanenitrile represented by formula (1) can be used include fragrance products such as perfumes and colognes; shampoos, conditioners, hair tonics, hair creams, mousses, gels, pomades, sprays, and other hair cosmetics; skin cosmetics such as lotions, beauty serums, creams, emulsions, packs, foundations, face powders, lipsticks, and various types of make-up; dishwashing detergents, laundry detergents, softeners, disinfectant detergents, deodorizing detergents, room air fresheners, furniture care products, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, bactericides, repellents, and other various health and hygiene detergents; quasi-drugs such as toothpaste, mouthwash, bath additives, antiperspirant products, and perm solution; miscellaneous goods such as toilet paper and tissue paper; pharmaceuticals; and foods.

[0045] The amount of 3-(4-alkylphenyl)propanenitrile represented by formula (1) in the above product is not particularly limited, and can be selected depending on the type, properties, and sensory effects of the product to be perfumed. For example, the amount of 3-(4-alkylphenyl)propanenitrile represented by formula (1) in the product is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.001% by mass or more. It is also preferably 80% by mass or less, even more preferably 60% by mass or less, and even more preferably 40% by mass or less. When the 3-(4-alkylphenyl)propanenitrile represented by formula (1) is used as an aroma oil, perfume, or the like, the amount of 3-(4-alkylphenyl)propanenitrile represented by formula (1) in the product may be 80% by mass or more, or may even be 100% by mass.

[0046] [Fragrance-Adding Method] The 3-(4-alkylphenyl)propanenitrile represented by the above general formula (1) has a floral scent and a green or fruity scent, and can therefore impart a floral scent and a green or fruity scent to various products. The present invention also includes a fragrance-adding method for imparting a floral scent and a green or fruity scent to a product using a 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1). Methods for imparting a floral scent and a green or fruity scent to a product include coating, spraying, immersion, etc., when the product is solid, and mixing, when the product is liquid. When imparting a floral scent and a green or fruity scent using a 3-(4-alkylphenyl)propanenitrile represented by formula (1), the 3-(4-alkylphenyl)propanenitrile represented by formula (1) may be used as one component of the fragrance composition to impart a floral scent and a green or fruity scent to various products.

[0047] In formula (1), R represents an alkyl group having 2 to 4 carbon atoms. Specifically, R is preferably at least one selected from the group consisting of an ethyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group, more preferably at least one selected from the group consisting of an isopropyl group, a normal butyl group, and an isobutyl group, and even more preferably a normal butyl group. When R is at least one selected from the group consisting of an ethyl group, an isopropyl group, a normal butyl group, an isobutyl group, and a tertiary butyl group, it is possible to impart a green or fruity scent in addition to a floral scent. When R is at least one selected from the group consisting of an isopropyl group and an isobutyl group, it is possible to impart a green and fruity scent in addition to a floral scent. When R is a normal butyl group, it is possible to impart a fruity and spicy scent in addition to a floral scent.

[0048] The 3-(4-alkylphenyl)propanenitrile represented by the above formula (1) has a floral fragrance and a green or fruity fragrance, and can therefore impart a floral fragrance, a green fragrance, or a fruity fragrance to various products. When R is an ethyl group, in particular, a green fragrance is imparted to a product in addition to a floral fragrance. When R is an isopropyl group, in particular, a green and fruity fragrance is imparted to a product in addition to a floral fragrance. When R is a normal butyl group, in particular, a fruity and spicy fragrance is imparted to a product in addition to a floral fragrance. Furthermore, the strength and diffusibility of the fragrance contained in the product can be significantly improved. When R is an isobutyl group, in particular, a green and fruity fragrance is imparted to a product in addition to a floral fragrance. When R is a tertiary butyl group, in particular, a green fragrance is imparted to a product in addition to a floral fragrance.

[0049] Examples of products to which a floral scent, a green scent, or a fruity scent can be imparted by the 3-(4-alkylphenyl)propanenitrile represented by formula (1) include fragrance products such as perfumes and colognes; shampoos, conditioners, hair tonics, hair creams, mousses, gels, pomades, sprays, and other hair cosmetics; skin cosmetics such as lotions, beauty serums, creams, emulsions, packs, foundations, face powders, lipsticks, and various types of make-up; dishwashing detergents, laundry detergents, softeners, disinfectant detergents, deodorizing detergents, room air fresheners, furniture care products, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, bactericides, repellents, and other various health and hygiene detergents; quasi-drugs such as toothpaste, mouthwash, bath additives, antiperspirant products, and perm solution; miscellaneous goods such as toilet paper and tissue paper; pharmaceuticals; and foods.

[0050] The amount of 3-(4-alkylphenyl)propanenitrile represented by formula (1) in the above product is not particularly limited, and can be selected depending on the type, properties, and sensory effects of the product to be perfumed. For example, the amount of 3-(4-alkylphenyl)propanenitrile represented by formula (1) in the product is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.001% by mass or more. It is also preferably 80% by mass or less, even more preferably 60% by mass or less, and even more preferably 40% by mass or less. When the 3-(4-alkylphenyl)propanenitrile represented by formula (1) is used as an aroma oil, perfume, or the like, the amount of 3-(4-alkylphenyl)propanenitrile represented by formula (1) in the product may be 80% by mass or more, or may even be 100% by mass.

[0051] [Method for producing 3-(4-alkylphenyl)propanenitrile] There are no limitations on the method for producing the 3-(4-alkylphenyl)propanenitrile contained as an active ingredient in the fragrance composition of the present invention, but it is preferable to obtain it by the production method shown below. As described above, the 3-(4-alkylphenyl)propanenitrile obtained by the production method shown below is also preferably used as a fragrance, and is also preferably used in the fragrance-imparting method. The production method shown below is also included in the present invention.

[0052] The method for producing 3-(4-alkylphenyl)propanenitrile of the present invention includes, in this order, a step of deriving cinnamonitrile represented by the following formula (4) by condensation reaction with acetonitrile using 4-alkylbenzaldehyde represented by the following formula (3) as a raw material, and a hydrogenation step. (In formulas (3) and (4), R represents an alkyl group having 2 to 4 carbon atoms.)

[0053] The reaction when 3-(4-alkylphenyl)propanenitrile is produced by the above-mentioned production method is shown in the following formula. (R represents an alkyl group having 1 to 4 carbon atoms.)

[0054] <Condensation Step> The production method includes a condensation step of dehydrating and condensing 4-alkylbenzaldehyde and acetonitrile. (R represents an alkyl group having 1 to 4 carbon atoms.)

[0055] The condensation reaction in this step preferably uses a basic compound as a catalyst. Examples of basic compounds used as catalysts include sodium hydroxide, potassium hydroxide, sodium bicarbonate, and mixtures thereof. The amount of the basic compound is preferably 0.05 equivalents or more, more preferably 0.1 equivalents or more, and even more preferably 0.2 equivalents or more, relative to 1 equivalent of the starting material dimethylbenzaldehyde, and is preferably 3 equivalents or less, more preferably 1 equivalent or less, and even more preferably 0.7 equivalents or less.

[0056] The amount of acetonitrile added is preferably 1 equivalent or more, more preferably 2 equivalents or more, and preferably 10 equivalents or less, more preferably 7 equivalents or less, relative to 1 equivalent of the raw material 4-alkylbenzaldehyde. The 4-alkylbenzaldehyde is preferably added stepwise or continuously over a period of time, for example, by dropwise addition.

[0057] The condensation reaction in this step can be carried out using acetonitrile as a solvent, but may also be carried out in the presence of other solvents. The solvent to be used is not particularly limited as long as it does not inhibit the condensation reaction, and examples thereof include hydrocarbon solvents such as alcohols such as methanol, ethanol, isopropanol, etc.; aliphatic hydrocarbons such as pentane, hexane, isopentane, heptane, octane, isooctane, etc.; and aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, etc. These may be used alone or in combination of two or more.

[0058] The reaction temperature in the condensation reaction of this step is not particularly limited, but from the viewpoint of reaction rate, it is preferably 0° C. or higher, more preferably 10° C. or higher, and from the viewpoint of suppressing side reactions, it is preferably 100° C. or lower, more preferably 70° C. or lower, and even more preferably 50° C. or lower. The reaction time is not particularly limited as long as it is a time that allows sufficient condensation to occur, but it is preferably 10 minutes or longer, more preferably 30 minutes or longer, even more preferably 1 hour or longer, and preferably 24 hours or shorter, more preferably 12 hours or shorter, even more preferably 6 hours or shorter, and even more preferably 3 hours or shorter.

[0059] The reaction can be stopped by neutralization, for example, by adding an acid such as acetic acid.

[0060] Furthermore, the method for isolating the intermediate represented by formula (3) from the solution after completion of the reaction is not particularly limited, and may be an appropriate combination of separation, extraction, and distillation purification. Alternatively, the intermediate may be used in a subsequent hydrogenation step without isolation. For example, the isolation method may involve adding a low-polarity or non-polar organic solvent to the solution after completion of the reaction to transfer the intermediate to an oil phase, drying the oil phase with, for example, magnesium sulfate, and then concentrating the filtrate obtained by filtration, followed by further distillation purification to isolate the intermediate.

[0061] <Hydrogenation Step> The production method described above has a hydrogenation step after the condensation step, to obtain 3-(4-alkylphenyl)propanenitrile represented by the formula (1).

[0062] This step is a step in which the intermediate represented by formula (4) obtained in the condensation step is hydrogenated to obtain the target product, 3-(4-alkylphenyl)propanenitrile represented by formula (1). The hydrogenation method is not particularly limited, and can be carried out by a known method using a hydrogenation catalyst.

[0063] The hydrogenation catalyst is not particularly limited, and known catalysts can be used. Examples of usable catalysts include supported heterogeneous hydrogenation catalysts in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, or diatomaceous earth; so-called Ziegler-type hydrogenation catalysts that use a transition metal salt such as an organic acid salt or an acetylacetone salt of Ni, Co, Fe, Cr, or the like, and a reducing agent such as organoaluminum; and homogeneous hydrogenation catalysts such as so-called organometallic complexes of organometallic compounds of Ti, Ru, Rh, Zr, or the like.

[0064] From the viewpoint of suppressing reactivity and side reactions, the temperature of the hydrogenation reaction in this step is preferably 0°C or higher, more preferably 10°C or higher, even more preferably 20°C or higher, and preferably 150°C or lower, even more preferably 100°C or lower. The pressure of hydrogen used in the hydrogenation reaction is preferably 0.01 MPaG or higher, more preferably 0.03 MPaG or higher, even more preferably 0.05 MPaG or higher, and preferably 10 MPaG or lower, more preferably 3 MPaG or lower, even more preferably 1 MPaG or lower, and still more preferably 0.5 MPaG or lower. The reaction time is not particularly limited, but is preferably 3 minutes or longer, more preferably 10 minutes or longer, even more preferably 30 minutes or longer, and preferably 24 hours or shorter, more preferably 12 hours or shorter, even more preferably 8 hours or shorter.

[0065] The hydrogenation reaction may be carried out in the presence of a solvent. The solvent to be used is not particularly limited as long as it does not inhibit the hydrogenation reaction, and examples thereof include hydrocarbon solvents such as alcohols such as methanol, ethanol, isopropanol, etc.; aliphatic hydrocarbons such as pentane, hexane, isopentane, heptane, octane, isooctane, etc.; and aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, etc. These may be used alone or in combination of two or more.

[0066] The method for purifying the target 3-(4-alkylphenyl)propanenitrile represented by formula (1) from the solution after completion of the reaction is not particularly limited, and any known method may be appropriately selected and used. Specific examples include filtration, chromatography, distillation purification, etc., and the target 3-(4-alkylphenyl)propanenitrile with high purity can be obtained by purifying the product by an appropriate combination of these methods.

[0067] The present invention will be specifically described based on the following examples, but the present invention is not limited to these examples.

[0068] <Analysis of Composition> The composition in each step described below, the composition of the product, and the composition of the composition were determined using gas chromatography (GC-2010Plus, manufactured by Shimadzu Corporation). The capillary column used was an HR-1701 (inner diameter 0.32 mmφ, length 30 m) manufactured by Shinwa Kako Co., Ltd. The temperature increase program was to increase the temperature from 100°C to 280°C at a rate of 5°C / min and hold the temperature for 30 minutes.

[0069] <NMR Spectral Analysis> Apparatus: Bruker AVANCE NEO 400 MHz Solvent: deuterated chloroform (CDCl3) Measurement mode: 1 H. 13 C Internal standard: tetramethylsilane (TMS)

[0070] <Evaluation of Fragrance and Fragrance Tone> The fragrance and fragrance tone of the nitrile compounds and fragrance compositions obtained in the examples were evaluated by impregnating filter paper 8 mm wide and 15 cm long with the samples and having expert panelists smell them.

[0071] [Production of 3-(4-alkylphenyl)propanenitrile] Example 1 (Production of 3-(4-ethylphenyl)propanenitrile) (Condensation Step) A 500 mL round-bottom flask equipped with a stirrer, a thermometer, and a dropping funnel was charged with acetonitrile (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 150.5 g) and potassium hydroxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 24.4 g). The temperature was raised to 50°C with stirring, and then 4-ethylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Co., Inc., 100.0 g) was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was maintained at 50°C for 2 hours to complete the reaction. Acetic acid was added to neutralize the mixture, and then water and heptane were added, and the aqueous phase was separated by liquid separation. Next, the heptane was distilled off to obtain a crude intermediate solution. This crude intermediate solution was subjected to simple distillation to obtain 3-(4-ethylphenyl)propenenitrile as an isomer mixture (42.0 g, total purity 99.3%).

[0072] (Hydrogenation Step) 3-(4-ethylphenyl)propenenitrile (41.0 g) obtained in the condensation step, 2-propanol (41.0 g), and a 5% palladium-carbon catalyst (N.E. Chemcat Corporation, hydrous product, PE type, 0.8 g) were charged into a 200 mL stainless steel autoclave equipped with a magnetic induction stirrer and capable of controlling the internal temperature using a jacket, and the hydrogenation reaction was carried out by stirring at 40°C and a hydrogen pressure of 0.4 MPa for 5 hours. The reaction solution was filtered to remove the catalyst, and heptane was added and the aqueous phase was separated by liquid separation. Next, the heptane was distilled off to obtain a crude product. The crude product was purified by column chromatography (silica gel, hexane:ethyl acetate=95:5) to obtain 3-(4-ethylphenyl)propanenitrile (20.0 g, purity 99.0%) as a colorless, transparent liquid. The content of 3-(2-ethylphenyl)propanenitrile was 0.04% by mass based on the mass of 3-(4-ethylphenyl)propanenitrile.

[0073] (Scent / Fragrance) Floral, Green, Mashroomy, Earthy (NMR spectrum) １ H-NMR (400MHz, CDCl ３) δ 1.23 (3H, t, J = 7.6Hz), 2.57-2.66 (4H, m), 2.92 (2H, t, J = 7.4Hz), 7.13-7.18 (4H, m) １３ C-NMR (100MHz, CDCl ３ ) δ 15.5, 19.4, 28.5, 31.2, 119.2, 128.2, 128.4, 135.3, 143.3

[0074] Example 2 (Production of 3-(4-isopropylphenyl)propanenitrile) (Condensation Step) A 500 mL round-bottom flask equipped with a stirrer, a thermometer, and a dropping funnel was charged with acetonitrile (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 135.1 g) and potassium hydroxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 22.2 g). The mixture was heated to 50°C with stirring, and then 4-isopropylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd., 100.0 g) was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was maintained at 50°C for 2 hours to complete the reaction. Acetic acid was added to neutralize the mixture, and then water and heptane were added, and the aqueous phase was separated by liquid separation. Next, the heptane was distilled off to obtain a crude intermediate solution. This crude intermediate solution was subjected to simple distillation to obtain 3-(4-isopropylphenyl)propenenitrile as an isomer mixture (53.0 g, total purity 98.3%).

[0075] (Hydrogenation Step) 3-(4-isopropylphenyl)propenenitrile (51.0 g) obtained in the condensation step, 2-propanol (51.0 g), and 5% palladium-carbon catalyst (N.E. Chemcat Corporation, hydrous product, PE type, 0.5 g) were charged into a 200 mL stainless steel autoclave equipped with a magnetic induction stirrer and capable of controlling the internal temperature using a jacket, and the hydrogenation reaction was carried out by stirring at 40°C and a hydrogen pressure of 0.4 MPa for 5 hours. The reaction solution was filtered to remove the catalyst, and heptane was added and the aqueous phase was separated by liquid separation. Next, the heptane was distilled off to obtain a crude product. The crude product was purified by column chromatography (silica gel, hexane:ethyl acetate=95:5) to obtain 3-(4-isopropylphenyl)propanenitrile (25.0 g, purity 99.0%) as a colorless, transparent liquid. The content of 3-(2-isopropylphenyl)propanenitrile was 0.2% by mass based on the mass of 3-(4-isopropylphenyl)propanenitrile.

[0076] (Scent / Fragrance) Floral, Green, Fruity, Rose, Muguet (NMR spectrum) １ H-NMR (400MHz, CDCl ３ ) δ 1.24 (6H, d, J = 6.9Hz), 2.6 (2H, t, J = 7.4), 2.86-2.94 (3H, m), 7.14-7.21 (4H, m) １３ C-NMR (100MHz, CDCl ３ ) δ 19.4, 24.0, 31.2, 33.8, 119.3, 126.9, 128.2, 135.4, 147.9

[0077] Example 3 (Production of 3-(4-normal butylphenyl)propanenitrile) (Condensation step) A 500 mL round-bottom flask equipped with a stirrer, a thermometer, and a dropping funnel was charged with acetonitrile (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 123.4 g) and potassium hydroxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 28.5 g). The temperature was raised to 50°C with stirring, and then 4-normal butylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Co., Inc., 100.0 g) was added dropwise over 2 hours. After completion of the dropwise addition, the temperature was maintained at 50°C for 2 hours to complete the reaction. Acetic acid was added to neutralize the mixture, and then water and heptane were added, and the aqueous phase was separated by liquid separation. Next, the heptane was distilled off to obtain a crude intermediate solution. This crude intermediate solution was subjected to simple distillation (160-162°C / 5 torr) to obtain 3-(4-n-butylphenyl)propenenitrile as an isomer mixture (64.0 g, total purity 98.5%).

[0078] (Hydrogenation Step) 3-(4-normal butylphenyl)propenenitrile (64.0 g) obtained in the condensation step, 2-propanol (64.0 g), and 5% palladium-carbon catalyst (N.E. Chemcat Corporation, hydrous product, PE type, 1.2 g) were charged into a 200 mL stainless steel autoclave equipped with a magnetic induction stirrer and capable of controlling the internal temperature using a jacket, and the hydrogenation reaction was carried out by stirring at 40°C and a hydrogen pressure of 0.4 MPa for 5 hours. The reaction liquid was filtered to remove the catalyst, and heptane was added and the aqueous phase was separated by liquid separation. Next, the heptane was distilled off to obtain a crude product. The crude product was rectified at 10 torr using a rectification column with 20 theoretical plates, and 3-(4-normal butylphenyl)propanenitrile (46.0 g, purity 99.0%) was obtained as a fraction at 160 to 166°C as a colorless, transparent liquid. The content of 3-(2-normal butylphenyl)propanenitrile was 0.7% by mass based on the mass of 3-(4-normal butylphenyl)propanenitrile.

[0079] (Aroma / Fragrance) Spicy, Floral, Futy, Lactonic (NMR spectrum) １ H-NMR (400MHz, CDCl ３) δ 0.92 (3H, t, J = 7.3Hz), 1.30-1.40 (2H, m), 1.55-1.62 (2H, m), 2.57-2.61 (4H, m), 2.92 (2H, t, J = 7.4Hz), 7.11-7.16 (4H, m) １３ C-NMR (100MHz, CDCl ３ ) δ 13.9, 19.4, 22.3, 31.2, 33.6, 35.2, 119.2, 128.1, 128.9, 135.2, 141.9

[0080] Example 4 (Production of 3-(4-isobutylphenyl)propanenitrile) (Condensation Step) A 500 mL round-bottom flask equipped with a stirrer, a thermometer, and a dropping funnel was charged with acetonitrile (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 123.5 g) and potassium hydroxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 20.5 g). The mixture was heated to 50°C with stirring, and then 4-isobutylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Co., Inc., 100.0 g) was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was maintained at 50°C for 2 hours to complete the reaction. After neutralization by adding acetic acid, water and heptane were added, and the aqueous phase was separated by liquid separation. Next, the heptane was distilled off to obtain a crude intermediate solution. This crude intermediate solution was subjected to simple distillation to obtain 3-(4-isobutylphenyl)propenenitrile as an isomer mixture (55.0 g, total purity 97.6%).

[0081] (Hydrogenation Step) 3-(4-isobutylphenyl)propenenitrile (53.0 g) obtained in the condensation step, 2-propanol (53.0 g), and a 5% palladium-carbon catalyst (N.E. Chemcat Corporation, hydrous product, PE type, 1.0 g) were charged into a 200 mL stainless steel autoclave equipped with a magnetic induction stirrer and capable of controlling the internal temperature using a jacket, and the hydrogenation reaction was carried out by stirring at 40°C and a hydrogen pressure of 0.4 MPa for 5 hours. The reaction liquid was filtered to remove the catalyst, and heptane was added and the aqueous phase was separated by liquid separation. Next, the heptane was distilled off to obtain a crude product. The crude product was purified by column chromatography (silica gel, hexane:ethyl acetate=95:5) to obtain 3-(4-isobutylphenyl)propanenitrile (22.0 g, purity 99.2%) as a colorless, transparent liquid. The content of 3-(2-isobutylphenyl)propanenitrile was 0.2% by mass based on the mass of 3-(4-isobutylphenyl)propanenitrile.

[0082] (Scent / Fragrance) Floral, Green, Fruity, Green, Muguet (NMR spectrum) １ H-NMR (400MHz, CDCl ３ )δ 0.90 (6H, d, J = 6.6Hz), 1.79-1.90 (1H, m), 2.45 (2H, d, J = 7.2Hz), 2.60 (2H, t, J = 7.5Hz), 2.93 (2H, t, J = 7.5Hz), 7.09-7.14 (4H, m) １３ C-NMR (100MHz, CDCl ３ ) δ 19.4, 22.3, 30.2, 31.3, 45.0, 119.2, 128.0, 129.6, 135.3, 140.7

[0083] Example 5 (Production of 3-(4-tert-butylphenyl)propanenitrile) (Condensation Step) A 500 mL round-bottom flask equipped with a stirrer, a thermometer, and a dropping funnel was charged with acetonitrile (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 123.3 g) and potassium hydroxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 24.4 g). The mixture was heated to 50°C with stirring, and then 4-tert-butylbenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd., 50.0 g) was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was maintained at 50°C for 2 hours to complete the reaction. Acetic acid was added to neutralize the mixture, and then water and heptane were added, and the aqueous phase was separated by liquid separation. Next, the heptane was distilled off to obtain a crude intermediate solution. This crude intermediate solution was subjected to simple distillation to obtain 3-(4-tert-butylphenyl)propenenitrile as an isomer mixture (19.7 g, total purity 94.1%).

[0084] (Hydrogenation Step) 3-(4-tert-butylphenyl)propenenitrile (19.7 g) obtained in the condensation step, methanol (40.0 g), and 5% palladium-carbon catalyst (N.E. Chemcat Corporation, hydrous product, PE type, 0.4 g) were charged into a 200 mL stainless steel autoclave equipped with a magnetic induction stirrer and capable of controlling the internal temperature using a jacket, and the hydrogenation reaction was carried out by stirring at 40°C and a hydrogen pressure of 0.4 MPa for 5 hours. The reaction solution was filtered to remove the catalyst, and heptane was added and the aqueous phase was separated by liquid separation. Next, the heptane was distilled off to obtain a crude product. The crude product was purified by column chromatography (silica gel, hexane:ethyl acetate=95:5) to obtain 3-(4-tert-butylphenyl)propanenitrile (6.4 g, purity 98.0%) as a colorless, transparent liquid. The content of 3-(2-tert-butylphenyl)propanenitrile was 0.6% by mass based on the mass of 3-(4-tert-butylphenyl)propanenitrile.

[0085] (Scent / Fragrance) Floral, Green, Woody, Peony, Musky (NMR spectrum) １ H-NMR (400MHz, CDCl ３) δ 1.31 (9H, s), 2.60 (2H, t, J = 7.5Hz), 2.93 (2H, t, J = 7.5Hz), 7.16 (2H, d, J = 8.4Hz), 7.35 (2H, d, J = 8.4) １３ C-NMR (100MHz, CDCl ３ ) δ 19.3, 31.1, 31.3, 34.5, 119.3, 125.8, 127.9, 135.0, 150.2

[0086] Comparative Example 1 (Production of 3-(4-methylphenyl)propanenitrile) (Condensation Step) A 500 mL round-bottom flask equipped with a stirrer, a thermometer, and a dropping funnel was charged with acetonitrile (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 167.8 g) and potassium hydroxide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 38.47 g). The mixture was heated to 50°C with stirring, and then 4-methylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd., 100.0 g) was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was maintained at 50°C for 2 hours to complete the reaction. After neutralization by adding acetic acid, water and heptane were added, and the aqueous phase was separated by separation. Next, the heptane was distilled off to obtain a crude intermediate solution (120.0 g, purity 81.6%) as a solid. The crude intermediate was used as is in the hydrogenation step.

[0087] (Hydrogenation Step) The crude intermediate (50.0 g) containing 3-(4-methylphenyl)propenenitrile obtained in the condensation step, methanol (50.0 g), and a 5% palladium-carbon catalyst (N.E. Chemcat Corporation, hydrous product, PE type, 1.0 g) were charged into a 200 mL stainless steel autoclave equipped with a magnetic induction stirrer and capable of controlling the internal temperature using a jacket, and the hydrogenation reaction was carried out by stirring at 40°C and a hydrogen pressure of 0.4 MPa for 5 hours. The reaction solution was filtered to remove the catalyst, and heptane was added and the aqueous phase was separated by liquid separation. Next, the heptane was distilled off to obtain a crude product. The crude product was purified by column chromatography (silica gel, hexane:ethyl acetate=95:5) to obtain 3-(4-methylphenyl)propanenitrile (18.0 g, purity 98.8%) as a colorless, transparent liquid. The content of 3-(2-methylphenyl)propanenitrile was 1.0% by mass based on the mass of 3-(4-methylphenyl)propanenitrile.

[0088] (Aroma / Fragrance) Green, Herbal, Floral, Spicy, Hyacinth (NMR spectrum) １ H-NMR (400MHz, CDCl ３ ) δ 2.33 (3H, s), 2.59 (2H, t, J = 7.4), 2.91 (2H, t, J = 7.4Hz), 7.10-7.15 (4H, m) １３ C-NMR (100MHz, CDCl ３ ) δ 19.5, 21.0, 31.2, 119.2, 128.1, 129.5, 135.0, 136.9

[0089] It is clear that the 3-(4-alkylphenyl)propanenitriles obtained in the Examples have a green or fruity scent in addition to a floral scent, and therefore can be suitably used as fragrances. Furthermore, it is clear that the 3-(4-alkylphenyl)propanenitriles obtained in the Examples can be suitably used in fragrance-imparting methods that impart a green or fruity scent in addition to a floral scent. In particular, it is clear that the 3-(4-isopropylphenyl)propanenitrile and 3-(4-isobutylphenyl)propanenitrile obtained in Examples 2 and 4 have a green and fruity scent in addition to a floral scent, and therefore can be more suitably used as fragrances and can be more suitably used in fragrance-imparting methods. Furthermore, it is clear that the 3-(4-n-butylphenyl)propanenitrile obtained in Example 3 has a fruity and spicy scent in addition to a floral scent, and therefore can be even more suitably used as a fragrance and can be even more suitably used in fragrance-imparting methods. On the other hand, the 3-(4-methylphenyl)propanenitrile obtained in Comparative Example 1 had a green scent and a herbal scent, but the floral scent was weak.

[0090] [Fragrance Composition] Example 6 (Apple-Cinnamon-Like Fragrance Composition) To the fragrance composition base shown in Table 1, 3-(4-n-butylphenyl)propanenitrile obtained in Example 3 was added so as to give 1.50% by mass, and the fragrance and fragrance tone were evaluated.

[0091] Comparative Example 2 (Apple-Cinnamon-Like Fragrance Composition) Cinnamalva ((E)-cinnamyl nitrile) was added to the fragrance composition base shown in Table 1 so as to give 1.50% by mass, and the fragrance and fragrance tone were evaluated.

[0092]

[0093] The fragrance composition of Example 6 had a stronger floral and fruity scent than the fragrance composition of Comparative Example 2, and was superior in scent strength and diffusibility.

[0094] Example 7 (Herb-like Fragrance Composition) To the fragrance composition base shown in Table 2, 3-(4-isopropylphenyl)propanenitrile obtained in Example 2 was added so as to give 10.0% by mass, and the fragrance and fragrance tone were evaluated.

[0095] Example 8 (Herb-like Fragrance Composition) To the fragrance composition base shown in Table 2, 3-(4-isobutylphenyl)propanenitrile obtained in Example 4 was added so as to give 10.0% by mass, and the fragrance and fragrance tone were evaluated.

[0096] Comparative Example 3 (Herb-like Fragrance Composition) To the fragrance composition base shown in Table 2, 10.0 mass % of dipropylene glycol (DPG) as a solvent was added to make the total mass % 18.0 mass %, and the fragrance and fragrance tone were evaluated.

[0097]

[0098] The fragrance composition of Example 7 had a stronger floral scent in the middle note and a stronger lilac-like floral feel than the fragrance composition of Comparative Example 3. The fragrance composition of Example 8 had a stronger floral scent in the middle note and a stronger geranium-like floral feel than the fragrance composition of Comparative Example 3.

[0099] Example 9 (Fragrance composition for fabric softener) To the fragrance composition base shown in Table 3, 3-(4-isopropylphenyl)propanenitrile obtained in Example 2 was added so as to give 6.5% by mass, and the fragrance and fragrance tone were evaluated.

[0100] Comparative Example 4 (Fragrance composition for fabric softener) To the fragrance composition base shown in Table 3, 6.5% by mass of dipropylene glycol (DPG) as a solvent was added to make the total mass 14.3% by mass, and the fragrance and fragrance tone were evaluated.

[0101]

[0102] The fragrance composition of Example 9 had a stronger floral body scent and a stronger lilac-like floral feel than the fragrance composition of Comparative Example 4.

[0103] Example 10 (Fragrance composition for hand cream) To the fragrance composition base shown in Table 4, 3-(4-isobutylphenyl)propanenitrile obtained in Example 4 was added so as to give 10.00% by mass, and the fragrance and fragrance tone were evaluated.

[0104] Comparative Example 5 (Fragrance composition for hand cream) To the fragrance composition base shown in Table 4, 10.00 mass% of dipropylene glycol (DPG) as a solvent was added to make the total mass 18.91 mass%, and the fragrance and fragrance tone were evaluated.

[0105]

[0106] The fragrance composition of Example 10 had a stronger floral scent than the fragrance composition of Comparative Example 5, and was herbal-rosy and geranium-like.

[0107] Example 11 (Rose-like Fragrance Composition) To the fragrance composition base shown in Table 5, 3-(4-ethylphenyl)propanenitrile obtained in Example 1 was added so as to give 7.5% by mass, and the fragrance and fragrance tone were evaluated.

[0108] Comparative Example 6 (Rose-like Fragrance Composition) To the fragrance composition base shown in Table 5, dipropylene glycol (DPG) as a solvent was added so as to give a concentration of 7.5 mass %, and the fragrance and fragrance tone were evaluated.

[0109]

[0110] The fragrance composition of Example 11 had a stronger floral scent than the fragrance composition of Comparative Example 6, and the floral scent also lingered.

[0111] As can be seen from the above results, the fragrance composition of the present invention has a strong floral odor. This indicates that 3-(4-alkylphenyl)propanenitrile can impart a floral odor, a green odor, or a fruity odor to a fragrance composition, and can further impart fragrance strength and diffusibility, making it useful as an active ingredient in fragrance compositions. Among these, fragrance compositions containing 3-(4-isobutylphenyl)propanenitrile or 3-(4-isopropylphenyl)propanenitrile are more preferred because they have a lilac-like or geranium-like floral scent. Furthermore, fragrance compositions containing 3-(4-normal butylphenyl)propanenitrile are even more preferred because they have a floral and fruity odor and are also excellent in fragrance strength and diffusibility.

Claims

1. A fragrance composition containing 3-(4-alkylphenyl)propanenitrile, represented by the following general formula (1), as an active ingredient. 【Chemistry 1】 (In formula (1), R represents an alkyl group having 2 to 4 carbon atoms.)

2. Furthermore, the fragrance composition according to claim 1 contains a fragrance substance other than 3-(4-alkylphenyl)propanenitrile represented by formula (1).

3. The fragrance composition according to claim 2, wherein the fragrance substance other than 3-(4-alkylphenyl)propanenitrile represented by formula (1) is at least one selected from the group consisting of hydrocarbons, alcohols, esters, phenols, aldehydes, ketones, acetals, ketals, ethers, natural essential oils, natural extracts, and nitriles other than 3-(4-alkylphenyl)propanenitrile represented by formula (1).

4. The fragrance composition according to any one of claims 1 to 3, wherein R is at least one selected from the group consisting of an ethyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a tert-butyl group.

5. The fragrance composition according to any one of claims 1 to 3, wherein R is at least one selected from the group consisting of an isopropyl group, a n-butyl group, and an isobutyl group.

6. A fragrance composition according to any one of claims 1 to 3, wherein R is a n-butyl group.

7. A fragrance composition according to any one of claims 1 to 3, comprising 0.03 to 0.8% by mass of 3-(2-alkylphenyl)propanenitrile represented by the following general formula (2) relative to 3-(4-alkylphenyl)propanenitrile represented by formula (1). 【Chemistry 2】 (In formula (2), R represents an alkyl group having 2 to 4 carbon atoms.)

8. Use of 3-(4-alkylphenyl)propanenitrile, represented by the following general formula (1), as a fragrance. 【Transformation 3】 (In formula (1), R represents an alkyl group having 2 to 4 carbon atoms.)

9. The use according to claim 8, wherein R is at least one selected from the group consisting of an ethyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a tert-butyl group.

10. The use according to claim 8 or 9, wherein the 3-(4-alkylphenyl)propanenitrile represented by formula (1) imparts a floral scent and a green or fruity scent.

11. The use according to claim 8 or 9, wherein R is at least one selected from the group consisting of isopropyl groups and isobutyl groups.

12. The use according to claim 11, wherein the 3-(4-alkylphenyl)propanenitrile represented by formula (1) imparts a floral, green, and fruity aroma.

13. The use according to claim 8 or 9, wherein R is a n-butyl group.

14. The use according to claim 13, wherein the 3-(4-alkylphenyl)propanenitrile represented by formula (1) imparts a floral, fruity, and spicy aroma.

15. A method for imparting a floral scent and a green or fruity scent using 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1). 【Chemistry 4】 (In formula (1), R represents an alkyl group having 2 to 4 carbon atoms.)

16. A method for producing 3-(4-alkylphenyl)propanenitrile, comprising the steps of: using 4-alkylbenzaldehyde represented by the following formula (3) as a raw material and converting it to cinnamonitrile represented by the following formula (4) through a condensation reaction with acetonitrile; and hydrogenation, in this order. 【Transformation 5】 (In formulas (3) and (4), R represents an alkyl group having 2 to 4 carbon atoms.)

17. A nitrile composition containing 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1) and 3-(2-alkylphenyl)propanenitrile represented by the following general formula (2), wherein the 3-(2-alkylphenyl)propanenitrile represented by the following general formula (2) is contained in an amount of 0.03 to 0.8% by mass relative to the 3-(4-alkylphenyl)propanenitrile represented by formula (1). 【Transformation 6】 (In formula (1), R represents an alkyl group having 2 to 4 carbon atoms. In formula (2), R represents an alkyl group having 2 to 4 carbon atoms.)

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