Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q13/00—Formulations or additives for perfume preparations
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C253/00—Preparation of carboxylic acid nitriles
  • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
  • C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
  • C07C255/07—Mononitriles
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B9/00—Essential oils; Perfumes

Definitions

• Nitrile compounds having a phenyl group are known as fragrance ingredients, such as peonyl (2-cyclohexylidene-2-phenylacetonitrile) having a grapefruit, geranium, or rose floral scent, and cinnamyl nitrile having a cinnamon or cassia scent (Non-Patent Document 1). It is known that some nitriles corresponding to aldehydes used as perfumes have similar fragrance notes. Non-Patent Document 2 describes a method for deriving aldehydes used as fragrances into the corresponding nitriles, and that the derived nitriles are useful as fragrance ingredients.
• an object of the present invention is to provide a fragrance composition having a novel fragrance and properties, use of a compound capable of imparting novel fragrance and properties to a fragrance composition, and a method for imparting fragrance.
• 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 that is useful as a fragrance, and thus completed the present invention.
• fragrance composition according to the above [2], wherein the fragrance substance other than the 3-(4-alkylphenyl)propanenitrile represented by the 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 the formula (1).
• R represents an alkyl group having 2 to 4 carbon atoms.
• a method for producing 3-(4-alkylphenyl)propanenitrile comprising the steps of: a step of converting a 4-alkylbenzaldehyde represented by the following formula (3) into cinnamonitrile represented by the following formula (4) through a condensation reaction with acetonitrile; and a hydrogenation step, in this order.
• a nitrile composition comprising 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), the 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).
• R represents an alkyl group having 2 to 4 carbon atoms.
• R represents an alkyl group having 2 to 4 carbon atoms.
• 3-(4-alkylphenyl)propanenitrile which can impart a floral fragrance and a green or fruity fragrance, as an active ingredient, it is possible to provide a fragrance composition having a strong floral fragrance. Furthermore, it is possible to provide the use of 3-(4-alkylphenyl)propanenitrile, which has 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.
• XX-YY means "XX or more and YY or less.”
• 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.
• R represents an alkyl group having 2 to 4 carbon atoms.
• the fragrance composition of the present invention contains 3-(4-alkylphenyl)propanenitrile, which has a floral scent and a green or fruity scent, as an active ingredient, and therefore has a strong floral scent and excellent fragrance strength. Therefore, it is useful as a fragrance component for various products.
• R represents an alkyl group having 2 to 4 carbon atoms.
• 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.
• 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 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 of a fragrance composition.
• R is at least one selected from the group consisting of an isopropyl group and an isobutyl group, it has a green scent and a fruity scent in addition to a floral scent, and can impart a strong floral scent, making it very useful as an active ingredient of a fragrance composition.
• R When R is a normal butyl group, it has a fruity scent and a spicy scent in addition to a floral scent, and can impart a strong floral scent, making it very useful as an active ingredient of a fragrance composition. Furthermore, when R is a normal butyl group, it can further significantly improve the strength and diffusibility of the scent of the fragrance composition.
• the 3-(4-alkylphenyl)propanenitrile represented by the above formula (1) is useful as an active ingredient of a fragrance composition, has a floral odor, and a green or fruity odor, can impart a strong floral odor, and can further impart odor strength and diffusibility.
• R is an ethyl group, it has a green scent in addition to a floral scent, and imparts a strong floral scent.
• R is an isopropyl group, it has a particularly floral scent, as well as a green scent and a fruity scent, and imparts a strong floral scent.
• R is a normal butyl group, it has a particularly floral fragrance, as well as a fruity fragrance and a spicy fragrance, and imparts a strong floral fragrance.
• R is an isobutyl group
• R has a floral scent, as well as a green scent and a fruity scent, and imparts a strong floral scent.
• R is a tertiary butyl group
• it has a green scent in addition to a floral scent, and imparts a strong floral scent.
• the fragrance composition of the present invention preferably contains 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 3-(2-alkylphenyl)propanenitrile represented by formula (2) results in a more complex and pleasant fragrance.
• R represents an alkyl group having 2 to 4 carbon atoms.
• R 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.
• R 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.
• 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.
• 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 of desired fragrance, the strength of the 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, even more preferably 1.0 to 20% by mass, and even more preferably 1.5 to 10% by mass.
• fragrance substances other than 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 fragrance substances other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1) are even more preferred.
• 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).
• a fragrance substance other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1) the fragrance can be adjusted to suit the target product. Also, by including a solvent, it becomes easy to dissolve and impregnate the target product, and the strength and persistence of the fragrance can be adjusted.
• fragrance substances other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1) there are no particular limitations on the fragrance substances other than the 3-(4-alkylphenyl)propanenitrile represented by formula (1) as long as they are conventionally known fragrance components, 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:
• the flavoring 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).
• 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, still more preferably at least one selected from the group consisting of alcohols, esters, phenols, and aldehydes, still more preferably at least one selected from the group consisting of esters and aldehydes, and still more preferably esters.
• Hydrocarbons include limonene, ⁇ -pinene, ⁇ -pinene, terpinene, cedrene, longifolene, valencene, etc.
• Alcohols include linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenol, ethyl linalool, farnesol, nerolidol, cis-3-hexenol, cedrol, menthol, borneol, ⁇ -phenylethyl alcohol, benzyl alcohol, phenylhexanol, 2,2,6-trimethylcyclohexyl-3-hexanol, 1-(2-t-butylcyclohexyloxy)-2-butanol, 4-isopropyl cyclohexanol, methylcyclohexyloxy ...
• Examples include cyclohexanemethanol, 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.
• Phenols include eugenol, thymol, vanillin, etc.
• 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, styraryl acetate, cinnamyl acetate, dimethylbenzylcarbinyl acetate, 3-pentyltetrahydropyran-4-yl acetate, citronellyl propionate, tricyclodecenyl propionate, pionate, allyl cycl
• 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- ⁇ -methylhydrocinnamic aldehyde, p-t-butylhydrocinnamic aldehyde, p-isopropyl- ⁇ -methylhydrocinnamic aldehyde, p-ethyl- ⁇ , ⁇ -dimethylhydrocinnamic aldehyde, ⁇ -amylcinnamic aldehyde, ⁇ -hexylcinnamic aldehyde, piperonal
• 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, ⁇ -methylionone, ⁇ -ionone, carvone, menthone, camphor, nootkatone, benzylacetone, anisylacetone, methyl ⁇ -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.
• Acetals and ketals include acetaldehyde ethyl phenylpropyl acetal, citral diethyl acetal, phenylacetaldehyde glycerin acetal, ethyl acetoacetate ethylene glycol ketal, etc.
• Ethers include anethole, ⁇ -naphthyl methyl ether, ⁇ -naphthyl ethyl ether, limonene oxide, rose oxide, 1,8-cineole, racemic or optically active dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan, etc.
• Lactones include ⁇ -nonalactone, ⁇ -undecalactone, ⁇ -decalactone, ⁇ -jasmolactone, coumarin, cyclopentadecanolide, cyclohexadecanolide, ambrettolide, ethylene brassylate, 11-oxahexadecanolide, etc.
• 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.
• nitriles than the 3-(4-alkylphenyl)propanenitrile represented by formula (1) include citronellyl nitrile, etc.
• the solvent examples include dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, and triethyl citrate.
• the surfactant may, for example, be polyoxyethylene lauryl sulfate ether.
• the fragrance composition containing the 3-(4-alkylphenyl)propanenitrile represented by the general formula (1) can be used as a fragrance component for various products.
• 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, beauty essences, creams, milky lotions, packs, foundations, face powders, lipsticks, and various types of make-up; dishwashing detergents, laundry detergents, softeners, disinfectant detergents, deodorizing detergents, indoor air fresheners, furniture care, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, germicides, 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
• the blending amount of the fragrance composition in the above-mentioned product is not particularly limited, and the blending amount of the fragrance composition can be selected depending on the type, properties, and sensory effect of the product to be scented.
• the blending 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. Also, it is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less.
• the amount of the fragrance composition in the product may be 80% by mass or more, or may be 100% by mass.
• the nitrile composition of the present invention contains 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1) and 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).
• R represents an alkyl group having 2 to 4 carbon atoms.
• formula (2) represents an alkyl group having 2 to 4 carbon atoms.
• the nitrile composition of the present invention contains 3-(4-alkylphenyl)propanenitrile, which has a floral fragrance and a green or fruity fragrance, as an active ingredient, and is considered to have a more complex and pleasant fragrance tone due to the inclusion of a small amount of 3-(2-alkylphenyl)propanenitrile represented by formula (2), and has a strong floral fragrance and excellent fragrance strength. Therefore, it is useful as a fragrance component for various products. It is also useful as a raw material for fragrance compositions.
• R represents an alkyl group having 2 to 4 carbon atoms.
• 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.
• 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 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 of a fragrance composition.
• R is at least one selected from the group consisting of an isopropyl group and an isobutyl group, it has a green scent and a fruity scent in addition to a floral scent, and can impart a strong floral scent, making it very useful as an active ingredient of a fragrance composition.
• R When R is a normal butyl group, it has a fruity scent and a spicy scent in addition to a floral scent, and can impart a strong floral scent, making it very useful as an active ingredient of a fragrance composition. Furthermore, when R is a normal butyl group, it can further significantly improve the strength and diffusibility of the scent of the fragrance composition.
• the 3-(4-alkylphenyl)propanenitrile represented by the above formula (1) is useful as an active ingredient of a fragrance composition, has a floral odor, and a green or fruity odor, can impart a strong floral odor, and can further impart odor strength and diffusibility.
• R is an ethyl group, it has a green scent in addition to a floral scent, and imparts a strong floral scent.
• R is an isopropyl group, it has a particularly floral scent, as well as a green scent and a fruity scent, and imparts a strong floral scent.
• R is a normal butyl group, it has a particularly floral fragrance, as well as a fruity fragrance and a spicy fragrance, and imparts a strong floral fragrance.
• R is an isobutyl group
• R has a floral scent, as well as a green scent and a fruity scent, and imparts a strong floral scent.
• R is a tertiary butyl group
• it has a green scent in addition to a floral scent, and imparts a strong floral scent.
• R represents an alkyl group having 2 to 4 carbon atoms.
• 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).
• 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.
• 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 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 of a fragrance composition.
• R is at least one selected from the group consisting of an isopropyl group and an isobutyl group, it has a green scent and a fruity scent in addition to a floral scent, and can impart a strong floral scent, making it very useful as an active ingredient of a fragrance composition.
• R When R is a normal butyl group, it has a fruity scent and a spicy scent in addition to a floral scent, and can impart a strong floral scent, making it very useful as an active ingredient of a fragrance composition. Furthermore, when R is a normal butyl group, it can further significantly improve the strength and diffusibility of the scent of the fragrance composition.
• the nitrile compound of the present invention contains 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, relative to 3-(4-alkylphenyl)propanenitrile represented by formula (1).
• the content of the nitrile composition in the fragrance composition may be appropriately adjusted depending on the type of fragrance composition, the type of desired fragrance, the strength of the 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, even more preferably 1.0 to 20% by mass, and even more preferably 1.5 to 10% by mass.
• 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1) has a floral scent and a green or fruity scent, and 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.
• R represents an alkyl group having 2 to 4 carbon atoms.
• R represents an alkyl group having 2 to 4 carbon atoms.
• 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.
• 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 therefore be more suitably used as a fragrance.
• R is at least one selected from the group consisting of an isopropyl group and an isobutyl group
• the compound has a green scent and a fruity scent in addition to a floral scent, and can therefore be used more preferably as a fragrance.
• R is a normal butyl group
• the compound has a fruity scent and a spicy scent in addition to a floral scent, and can therefore be used even more preferably as a fragrance.
• R When R is an ethyl group, it has a green scent in addition to a floral scent. When R is an isopropyl group, it has a floral scent, as well as a green and fruity scent. When R is a normal butyl group, the compound has a floral fragrance as well as a fruity and spicy fragrance. When R is an isobutyl group, it has a floral scent as well as a green and fruity scent. When R is a tertiary butyl group, it has a green scent in addition to a floral scent.
• the 3-(4-alkylphenyl)propanenitrile represented by the above formula (1) has a floral fragrance, a green fragrance, or a fruity fragrance. Therefore, the use of the 3-(4-alkylphenyl)propanenitrile represented by the formula (1) imparts a floral fragrance, a green fragrance, or a fruity fragrance to a product. In addition, the strength and diffusibility of the fragrance contained in the product can be improved.
• R is an ethyl group, it imparts a green scent in addition to a floral scent.
• R is an isopropyl group, it imparts a floral scent, as well as a green and fruity scent.
• R When R is a normal butyl group, it imparts a fruity and spicy scent in addition to a floral scent, and further improves the strength and diffusibility of the scent contained in the product. When R is an isobutyl group, it imparts a floral scent as well as a green and fruity scent. When R is a tertiary butyl group, it imparts a green scent in addition to a floral scent.
• the 3-(4-alkylphenyl)propanenitrile represented by formula (1) can be used as a fragrance component of various products.
• the 3-(4-alkylphenyl)propanenitrile represented by formula (1) is used as a fragrance component of 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 the formula (1) can be used include fragrance products such as perfumes and colognes; shampoos, rinses, hair tonics, hair creams, mousses, gels, pomades, sprays, and other hair cosmetics; skin cosmetics such as lotions, beauty essences, creams, milky lotions, packs, foundations, face powders, lipsticks, and various types of make-up; dishwashing detergents, laundry detergents, softeners, disinfectant detergents, deodorizing detergents, room fresheners, furniture care, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, germicides, repellents, and other various health and hygiene detergents; quasi-drugs such as toothpaste, mouthwash, bath additives, antiperspirant products, and perm solutions; miscellaneous goods such as toilet paper and tissue paper; medicines, and the like; and foods, and the like.
• fragrance products such as perfumes and cologne
• 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 scented.
• 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. Also, it is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less.
• the amount of the 3-(4-alkylphenyl)propanenitrile represented by the formula (1) in the product may be 80 mass% or more, or may be 100 mass%.
• the 3-(4-alkylphenyl)propanenitrile represented by the above general formula (1) has a floral fragrance and a green or fruity fragrance, and can impart a floral fragrance and, in addition, a green or fruity fragrance to various products.
• the present invention also includes a fragrance imparting method for imparting a floral fragrance and a green or fruity fragrance by using the 3-(4-alkylphenyl)propanenitrile represented by the following general formula (1).
• a method for imparting a floral odor and, in addition, a green odor or a fruity odor to a product when the product is solid, coating, spraying, immersion, etc. may be performed, and when the product is liquid, mixing may be performed.
• the 3-(4-alkylphenyl)propanenitrile represented by formula (1) may be used as one component of the fragrance composition to impart a floral odor and a green odor or a fruity odor to various products.
• R represents an alkyl group having 2 to 4 carbon atoms.
• 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.
• 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.
• 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 scent and a fruity scent in addition to a floral scent.
• R is a normal butyl group, in addition to a floral scent, a fruity scent and a spicy scent can be imparted.
• the 3-(4-alkylphenyl)propanenitrile represented by the above formula (1) has a floral odor, a green odor or a fruity odor, and can impart a floral odor, a green odor or a fruity odor to various products.
• R is an ethyl group, it particularly imparts a green scent to the product in addition to a floral scent.
• R is an isopropyl group, it particularly imparts a floral, as well as a green and fruity, scent to the product.
• R is a normal butyl group, it imparts a fruity and spicy fragrance to the product in addition to a floral fragrance, and further improves the strength and diffusibility of the fragrance contained in the product.
• R is an isobutyl group
• R particularly imparts a floral, as well as a green and fruity, scent to the product.
• R particularly imparts a green scent to the product in addition to a floral scent.
• Products that can be imparted with a floral, green or fruity scent by the 3-(4-alkylphenyl)propanenitrile represented by formula (1) include, for example, fragrance products such as perfumes and colognes; shampoos, rinses, hair tonics, hair creams, mousses, gels, pomades, sprays and other hair cosmetics; skin cosmetics such as lotions, beauty essences, creams, milky lotions, packs, foundations, face powders, lipsticks and various types of make-up; dishwashing detergents, laundry detergents, softeners, disinfectant detergents, deodorizing detergents, room fresheners, furniture care, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, germicides, repellents and other various health and hygiene detergents; toothpaste, mouthwash, bath additives, antiperspirant products, perm solution and other quasi-drugs; miscellaneous goods such as toilet paper and tissue paper; medicines and the like; and foods and the like.
• fragrance products such
• 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 scented.
• 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. Also, it is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less.
• the amount of the 3-(4-alkylphenyl)propanenitrile represented by the formula (1) in the product may be 80 mass% or more, or may be 100 mass%.
• 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 a condensation reaction with acetonitrile using 4-alkylbenzaldehyde represented by the following formula (3) as a raw material, and a hydrogenation step.
• R represents an alkyl group having 2 to 4 carbon atoms.
• the above-mentioned 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.
• the condensation reaction in this step is preferably carried out using a basic compound as a catalyst.
• the basic compound used as a catalyst include sodium hydroxide, potassium hydroxide, sodium bicarbonate, a mixture thereof, etc.
• 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 raw material dimethylbenzaldehyde, and is preferably 3 equivalents or less, more preferably 1 equivalent or less, and even more preferably 0.7 equivalents or less.
• 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.
• 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, but examples 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.
• 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 the condensation is sufficiently carried out, but is preferably 10 minutes or more, more preferably 30 minutes or more, even more preferably 1 hour or more, and is preferably 24 hours or less, more preferably 12 hours or less, even more preferably 6 hours or less, and even more preferably 3 hours or less.
• the reaction can be stopped by neutralization, for example by adding an acid such as acetic acid.
• the method for isolating the intermediate represented by the formula (3) from the solution after the completion of the reaction is not particularly limited, and may be a suitable combination of separation, extraction, and distillation purification.
• the intermediate may be used in the subsequent hydrogenation step without being isolated.
• isolation for example, a method of 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 obtained oil phase with, for example, magnesium sulfate, and then concentrating the filtrate obtained by filtration, and further purifying it by distillation, can be used to isolate the intermediate.
• the above-mentioned production method includes a hydrogenation step after the condensation step, and obtains the 3-(4-alkylphenyl)propanenitrile represented by the above-mentioned formula (1).
• the intermediate represented by formula (4) obtained in the condensation step is hydrogenated to obtain the desired product, 3-(4-alkylphenyl)propanenitrile represented by formula (1).
• the hydrogenation method is not particularly limited, but can be performed by a known method using a hydrogenation catalyst.
• the hydrogenation catalyst is not particularly limited, and known catalysts can be used.
• supported heterogeneous hydrogenation catalysts in which metals such as Ni, Pt, Pd, Ru, etc. are supported on carbon, silica, alumina, diatomaceous earth, etc.
• so-called Ziegler-type hydrogenation catalysts that use transition metal salts such as organic acid salts or acetylacetone salts of Ni, Co, Fe, Cr, etc. and reducing agents such as organoaluminum
• homogeneous hydrogenation catalysts such as so-called organometallic complexes of organometallic compounds such as Ti, Ru, Rh, Zr, etc. can be used.
• the temperature of the hydrogenation reaction in this step is, from the viewpoint of suppressing reactivity and side reactions, preferably 0° C. or higher, more preferably 10° C. or higher, even more preferably 20° C. or higher, and is 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 more, more preferably 0.03 MPaG or more, even more preferably 0.05 MPaG or more, and preferably 10 MPaG or less, more preferably 3 MPaG or less, even more preferably 1 MPaG or less, and still more preferably 0.5 MPaG or less.
• the reaction time is not particularly limited, but is preferably 3 minutes or more, more preferably 10 minutes or more, and even more preferably 30 minutes or more, and is preferably 24 hours or less, more preferably 12 hours or less, and even more preferably 8 hours or less.
• 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, but examples 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.
• 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 carried out. Specific examples include filtration, chromatography, distillation purification, etc., and the target 3-(4-alkylphenyl)propanenitrile with high purity can be obtained by purifying using an appropriate combination of these.
• composition in each step, the composition of the product, and the composition of the composition described below were determined using gas chromatography (GC-2010Plus, manufactured by Shimadzu Corporation).
• the capillary column used was HR-1701 (inner diameter 0.32 mm ⁇ , 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.
• fragrance and fragrance tone of the nitrile compounds and fragrance compositions obtained in the Examples were evaluated by impregnating them into a filter paper 8 mm wide and 15 cm long and having a specialized panel smell them.
• Example 1 [Production of 3-(4-alkylphenyl)propanenitrile]
• Example 1 (Production of 3-(4-ethylphenyl)propanenitrile) (Condensation step)
• acetonitrile manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 150.5 g
• potassium hydroxide manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 24.4 g
• the temperature was raised to 50°C while stirring, and then 4-ethylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd., 100.0 g) was dropped over 2 hours.
• heptane was distilled off to obtain a crude product.
• the 3-(2-ethylphenyl)propanenitrile was contained in an amount of 0.04% by mass relative to the 3-(4-ethylphenyl)propanenitrile.
• Example 2 (Production of 3-(4-isopropylphenyl)propanenitrile) (Condensation step)
• a round-bottom flask with an internal volume of 500 mL 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), and the temperature was raised to 50°C while stirring, and then 4-isopropylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd., 100.0 g) was dropped over 2 hours.
• Example 3 (Production of 3-(4-n-butylphenyl)propanenitrile) (Condensation step)
• a round-bottom flask with an internal volume of 500 mL 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), and the temperature was raised to 50°C while stirring, and then 4-n-butylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd., 100.0 g) was dropped over 2 hours.
• Example 4 (Production of 3-(4-isobutylphenyl)propanenitrile) (Condensation step)
• a round-bottom flask with an internal volume of 500 mL 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), and the temperature was raised to 50° C. with stirring, and then 4-isobutylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd., 100.0 g) was dropped over 2 hours.
• Example 5 (Production of 3-(4-tert-butylphenyl)propanenitrile) (Condensation step)
• Comparative Example 1 Production of 3-(4-methylphenyl)propanenitrile (Condensation step) A round-bottom flask with an internal volume of 500 mL 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), and the temperature was raised to 50°C while stirring, and then 4-methylbenzaldehyde (manufactured by Mitsubishi Gas Chemical Co., Ltd., 100.0 g) was dropped over 2 hours.
• acetonitrile manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 167.8 g
• potassium hydroxide manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., 38.47 g
• the 3-(4-alkylphenyl)propanenitrile obtained in the Examples has a green or fruity odor in addition to a floral odor, and therefore can be suitably used as a fragrance. It is further understood that the 3-(4-alkylphenyl)propanenitrile obtained in the Examples can be suitably used in a fragrance method that imparts a green or fruity odor in addition to a floral odor.
• 3-(4-isopropylphenyl)propanenitrile and 3-(4-isobutylphenyl)propanenitrile obtained in Examples 2 and 4 have a green odor and a fruity odor in addition to a floral odor, and therefore can be more suitably used as a fragrance and more suitably used in a fragrance-imparting method.
• the 3-(4-n-butylphenyl)propanenitrile obtained in Example 3 has a fruity odor and a spicy odor in addition to a floral odor, it can be more suitably used as a fragrance and more suitably used in a fragrance application method.
• the 3-(4-methylphenyl)propanenitrile obtained in Comparative Example 1 had a green scent and a herbal scent, and the floral scent was weak.
• 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 a concentration of 1.50 mass %, and the fragrance and fragrance tone were evaluated.
• Comparative Example 2 (Apple/Cinnamon-like Fragrance Composition) To the fragrance composition base shown in Table 1, CINNAMALVA ((E)-cinnamyl nitrile) was added so as to give a concentration of 1.50% by mass, and the fragrance and fragrance tone were evaluated.
• 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 fragrance strength and diffusibility.
• Example 7 (Herbal 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 a concentration of 10.0 mass %, and the fragrance and fragrance tone were evaluated.
• Example 8 (Herbal 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 a concentration of 10.0 mass %, and the fragrance and fragrance tone were evaluated.
• Comparative Example 3 (Herbal Flavor Composition) To the fragrance composition base shown in Table 2, 10.0% by mass of dipropylene glycol (DPG) as a solvent was added to make the total amount 18.0% by mass, and the fragrance and fragrance tone were evaluated.
• DPG dipropylene glycol
• the fragrance composition of Example 7 had a stronger floral scent in the middle notes 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 notes and a stronger geranium-like floral feel than the fragrance composition of Comparative Example 3.
• 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 a concentration of 6.5% by mass, and the fragrance and fragrance tone were evaluated.
• 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.
• 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 a concentration of 10.00 mass %, and the fragrance and fragrance tone were evaluated.
• Comparative Example 5 Frarance composition for hand cream
• DPG dipropylene glycol
• the fragrance composition of Example 10 Compared to the fragrance composition of Comparative Example 5, the fragrance composition of Example 10 had a stronger floral scent and a herbal-rosy geranium-like scent.
• 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 a concentration of 7.5% by mass, and the fragrance and fragrance tone were evaluated.
• the fragrance composition of Example 11 had a stronger floral scent than the fragrance composition of Comparative Example 6, and the lingering scent also had a floral scent.
• the fragrance composition of the present invention has a strong floral odor.
• 3-(4-alkylphenyl)propanenitrile can impart a floral odor, a green odor, or a fruity odor to a fragrance composition, and can further impart odor strength and diffusibility, and is therefore useful as an active ingredient of a fragrance composition.
• a fragrance composition containing 3-(4-isobutylphenyl)propanenitrile or 3-(4-isopropylphenyl)propanenitrile is more preferred since it has a lilac-like or geranium-like floral scent.
• a fragrance composition containing 3-(4-n-butylphenyl)propanenitrile is more preferred since it has a floral and fruity scent and is also excellent in scent strength and diffusibility.

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