Fragrance composition, and method for producing 1-ethylcyclohexanecarboxylic acid ester

Abstract

Provided are: a fragrance composition containing a 1-ethylcyclohexanecarboxylic acid ester represented by general formula (1) as an active ingredient; a use of a 1-ethylcyclohexanecarboxylic acid ester as a fragrance ingredient; and a method for producing a 1-ethylcyclohexanecarboxylic acid ester. The fragrance composition contains, as an active ingredient, a 1-ethylcyclohexanecarboxylic acid ester that can impart a herbal aroma and can achieve aroma diffusibleness, and therefore has excellent herbal flavor and aroma diffusibleness. (In formula (1), R1 represents an alkyl group having 1 to 3 carbon atoms.)

Description

Fragrance composition and method for producing 1-ethylcyclohexanecarboxylic acid ester

[0001] The present invention relates to a fragrance composition and a method for producing a 1-ethylcyclohexanecarboxylic acid ester.

[0002] Ester compounds are widely used as fragrances. In particular, formate esters and acetate esters are widely found in nature, and many of them have a fruity scent. Synthetic fragrances that are ester compounds are also known. For example, Non-Patent Document 1 describes that methyl 1-methyl-3-cyclohexenecarboxylate has a complex scent reminiscent of chrysanthemum or thujone and is used as a fragrance.

[0003] Genichi Indo, "Revised and Expanded Edition of Synthetic Fragrances: Chemistry and Product Knowledge," 1996, 672 pages, Chemical Daily Press

[0004] As described above, many ester compounds are used as natural or synthetic fragrances. However, 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 fragrance components that exhibit excellent effects, particularly when mixed with other fragrances, are in demand. Furthermore, because fragrances are also affected by impurities and other factors generated during the manufacturing process, there is a need for a manufacturing method that is industrially practical yet capable of producing fragrances with excellent fragrances. Therefore, an object of the present invention is to provide a fragrance composition having novel fragrances and properties, as well as a use of a compound that can impart novel fragrances and properties to a fragrance composition, a fragrance imparting method, and a manufacturing method for said compound.

[0005] The present inventors have discovered that a fragrance composition containing a specific ester compound as an active ingredient has a novel fragrance and properties, that the ester compound is excellent as a fragrance, and an efficient method for producing the ester compound, 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, a 1-ethylcyclohexanecarboxylic acid ester represented by the following general formula (1): (In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms.) [2] The fragrance composition according to [1] above, further comprising a fragrance substance other than the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1). [3] The fragrance composition according to [2] above, wherein the fragrance substance other than the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1) is at least one selected from the group consisting of hydrocarbons, alcohols, phenols, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, natural essential oils, natural extracts, and esters other than the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1). [4] R 1 [5] The fragrance composition according to any one of [1] to [3] above, wherein R is at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. 1 [6] Use of a 1-ethylcyclohexanecarboxylic acid ester represented by the following general formula (1) as a fragrance. (In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms.) [7] R 1 is at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. [8] The use according to the above [6] or [7], wherein the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1) imparts a herbal fragrance. [9] R 1 is an ethyl group.

[10] The use according to any one of [6] to [8] above, wherein a 1-ethylcyclohexanecarboxylic acid ester represented by formula (1) imparts a herbal fragrance and a fruity fragrance.

[11] A fragrance-imparting method, comprising imparting a herbal fragrance with a 1-ethylcyclohexanecarboxylic acid ester represented by the following formula (1a): (In formula (1a), R 2 represents at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. 2is an ethyl group, and the 1-ethylcyclohexanecarboxylic acid ester represented by the formula (1a) imparts a herbal fragrance and a fruity fragrance.

[13] A method for producing a 1-ethylcyclohexanecarboxylic acid ester, comprising reacting a compound represented by the following general formula (2) with carbon monoxide and an alcohol represented by the following general formula (3) in the presence of hydrogen fluoride to obtain a 1-ethylcyclohexanecarboxylic acid ester represented by the following general formula (1): (In formula (2), one of the carbon-carbon bonds including the dashed line is a double bond and the others are single bonds. In formula (3), R 1 represents an alkyl group having 1 to 3 carbon atoms. 1 is R in formula (3) 1 and represents an alkyl group having 1 to 3 carbon atoms.)

[14] R 1

[15] The method for producing a 1-ethylcyclohexanecarboxylic acid ester according to

[13] above, wherein R is at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. 1 is an ethyl group.

[16] The method for producing a 1-ethylcyclohexanecarboxylic acid ester according to any one of the above

[13] to

[15] , wherein the compound represented by the general formula (2) is at least one selected from the group consisting of vinylcyclohexane and 4-ethylcyclohexene.

[17] The method for producing a 1-ethylcyclohexanecarboxylic acid ester according to any one of the above

[13] to

[16] , comprising a step of hydrogenating 4-vinylcyclohexene to obtain 4-ethylcyclohexene, wherein the compound represented by the general formula (2) is 4-ethylcyclohexene.

[0007] According to the present invention, it is possible to provide a fragrance composition that has a herbal feel and excellent fragrance diffusibility by containing, as an active ingredient, a 1-ethylcyclohexanecarboxylic acid ester that can impart a herbal fragrance and further impart fragrance diffusibility, as well as use of the 1-ethylcyclohexanecarboxylic acid ester as a fragrance and a method for producing the 1-ethylcyclohexanecarboxylic acid ester.

[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, as an active ingredient, a 1-ethylcyclohexanecarboxylic acid ester represented by the following general formula (1). (In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms.)

[0010] The fragrance composition of the present invention can impart a herbal fragrance and, since it contains 1-ethylcyclohexanecarboxylic acid ester as an active ingredient, which can impart fragrance diffusibility, has a herbal feel and excellent fragrance diffusibility, and is therefore useful as a fragrance component for various products.

[0011] <1-Ethylcyclohexanecarboxylic acid ester> In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms. 1 is preferably at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, more preferably at least one selected from the group consisting of a methyl group and an ethyl group, and even more preferably an ethyl group. 1 When the group is an ethyl group, it has a fruity scent in addition to a herbal scent, and is therefore very useful as an active ingredient in a fragrance composition.

[0012] The 1-ethylcyclohexanecarboxylic acid ester represented by the above formula (1) is useful as an active ingredient of a fragrance composition, has a herbal fragrance, can impart a herbal fragrance to the fragrance composition, and can also impart fragrance diffusibility. 1 When R is a methyl group, it has a particularly easily diffusible herbal fragrance. 1 When R is an ethyl group, it has a particularly easily diffusible herbal and fruity fragrance. 1 When R is an n-propyl group, it has a particularly easily diffusible herbal fragrance. 1 When is an isopropyl group, it has a particularly easily diffusible herbal scent.

[0013] The content of the 1-ethylcyclohexanecarboxylic acid ester 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 0.02 to 30% by mass, even more preferably 0.05 to 20% by mass, still more preferably 0.1 to 10% by mass, still more preferably 0.5 to 10% by mass, and even more preferably 0.8 to 7% by mass.

[0014] <Other Components and Products in Which the 1-ethylcyclohexane carboxylic acid ester can be used> Examples of other components, other than the 1-ethylcyclohexane carboxylic acid ester, that may be contained in the fragrance composition containing the 1-ethylcyclohexane carboxylic acid ester include fragrance substances other than the 1-ethylcyclohexane carboxylic acid ester represented by Formula (1), surfactants, solvents, antioxidants, and colorants. At least one selected from the group consisting of fragrance substances other than the 1-ethylcyclohexane carboxylic acid ester 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 1-ethylcyclohexane carboxylic acid ester represented by Formula (1) and solvents is more preferred, and a fragrance substance other than the 1-ethylcyclohexane carboxylic acid ester represented by Formula (1) is even more preferred. That is, a preferred fragrance composition of the present invention contains the 1-ethylcyclohexane carboxylic acid ester represented by Formula (1) as an active ingredient and also contains a fragrance substance other than the 1-ethylcyclohexane carboxylic acid ester represented by Formula (1). By including a fragrance substance other than the 1-ethylcyclohexane carboxylic acid ester represented by Formula (1), the scent can be adjusted to suit the desired product. Furthermore, the inclusion of a solvent makes it easier to dissolve and impregnate the target product, and allows the intensity and persistence of the fragrance to be adjusted. In particular, it is preferable to compose a floral-type fragrance composition using a fragrance substance other than the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1), and it is preferable to contain the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1) as an active ingredient in the floral-type fragrance composition.

[0015] The fragrance substance other than the 1-ethylcyclohexanecarboxylic acid ester 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:

[0016] The fragrance substance other than the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1) is preferably at least one selected from the group consisting of hydrocarbons, alcohols, phenols, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, natural essential oils, natural extracts, and esters other than the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1), more preferably at least one selected from the group consisting of alcohols, aldehydes, and esters other than the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1), and even more preferably at least one selected from the group consisting of alcohols and aldehydes.

[0017] Examples of hydrocarbons include limonene, α-pinene, β-pinene, terpinene, cedrene, longifolene, valencene, etc. 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, methyl ... Examples of phenols include 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. Examples of phenols include eugenol, thymol, and vanillin.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 methylphenyl glycidate, methyl anthranilate, fultate, and the like.

[0018] 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. 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. Examples of acetals and ketals include acetaldehyde ethyl phenylpropyl acetal, citral diethyl acetal, phenylacetaldehyde glycerin acetal, ethyl acetoacetate ethylene glycol ketal, etc. 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, etc. Examples of nitriles include citronellyl nitrile, etc.Examples of lactones include γ-nonalactone, γ-undecalactone, σ-decalactone, γ-jasmolactone, coumarin, cyclopentadecanolide, cyclohexadecanolide, ambrettelide, ethylene brassylate, 11-oxahexadecanolide, etc. Examples of natural essential oils and natural 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, labdanum, etc.

[0019] 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.

[0020] The fragrance composition containing the 1-ethylcyclohexanecarboxylic acid ester 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. Among these, the fragrance composition containing the 1-ethylcyclohexanecarboxylic acid ester represented by the general formula (1) is preferably used in toiletry products such as laundry cleansers and body cleansers.

[0021] 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.

[0022] [Use as a fragrance] The 1-ethylcyclohexanecarboxylic acid ester represented by the following general formula (1) has an excellent herbal fragrance and can be used as a fragrance. The use of the 1-ethylcyclohexanecarboxylic acid ester represented by the following general formula (1) as a fragrance is also included in the present invention. (In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms.)

[0023] In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms. 1 is preferably at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, more preferably at least one selected from the group consisting of a methyl group and an ethyl group, and even more preferably an ethyl group. 1 When is an ethyl group, the compound has a fruity scent in addition to a herbal scent, and can therefore be more suitably used as a fragrance.

[0024] The 1-ethylcyclohexanecarboxylic acid ester represented by the above formula (1) has an excellent herbal fragrance. Therefore, the use of the 1-ethylcyclohexanecarboxylic acid ester represented by the formula (1) imparts a herbal fragrance. 1 When R is an ethyl group, it has a fruity scent in addition to a herbal scent. 1When R is an ethyl group, the use of 1-ethylcyclohexanecarboxylic acid ester represented by formula (1) imparts herbal and fruity fragrances. 1 When R is a methyl group, it has a particularly easily diffusible herbal fragrance. 1 When R is an ethyl group, it has a particularly easily diffusible herbal and fruity fragrance. 1 When R is an n-propyl group, it has a particularly easily diffusible herbal fragrance. 1 When is an isopropyl group, it has a particularly easily diffusible herbal scent.

[0025] The 1-ethylcyclohexanecarboxylic acid ester represented by formula (1) can be used as a fragrance component for various products. When the 1-ethylcyclohexanecarboxylic acid ester 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 1-ethylcyclohexane carboxylic acid ester 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.

[0026] The amount of the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1) in the 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 the 1-ethylcyclohexanecarboxylic acid ester 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 1-ethylcyclohexanecarboxylic acid ester represented by formula (1) is used as an aroma oil, perfume, or the like, the amount of the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1) in the product may be 80% by mass or more, or even 100% by mass.

[0027] [Fragrance-imparting method] 1-ethylcyclohexanecarboxylic acid esters represented by the following general formula (1a) have an excellent herbal fragrance and can therefore impart a herbal fragrance to a variety of products. The present invention also includes a fragrance-imparting method in which a herbal fragrance is imparted using a 1-ethylcyclohexanecarboxylic acid ester represented by the following general formula (1a). As a method for imparting a herbal fragrance to a product, if the product is solid, coating, spraying, immersion, etc. may be performed, and if the product is liquid, mixing may be performed. Note that when a herbal fragrance is imparted using a 1-ethylcyclohexanecarboxylic acid ester represented by formula (1a), the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1a) may be used as one component of the fragrance composition to impart a herbal fragrance to a variety of products. (In formula (1a), R 2 represents at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

[0028] In formula (1a), R 1is at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, more preferably at least one selected from the group consisting of a methyl group and an ethyl group, and even more preferably an ethyl group. 1 When the alkyl group is an ethyl group, it has a fruity scent in addition to a herbal scent, and therefore can impart both a herbal scent and a fruity scent to a variety of products.

[0029] The 1-ethylcyclohexanecarboxylic acid ester represented by the above formula (1a) has an excellent herbal fragrance and can impart herbal fragrance to a variety of products. 1 When R is an ethyl group, it has a fruity scent in addition to a herbal scent. 1 When R is an ethyl group, the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1a) can impart herbal and fruity scents to various products. 1 When R is a methyl group, it has a particularly easily diffusible herbal fragrance and imparts a herbal fragrance to the product. 1 When R is an ethyl group, it has a particularly easily diffusible herbal and fruity fragrance, imparting herbal and fruity fragrances to the product. 1 When R is an n-propyl group, it has a particularly easily diffusible herbal fragrance and imparts a herbal fragrance to the product. 1 When is an isopropyl group, it has a particularly easily diffusible herbal fragrance and imparts a herbal fragrance to the product.

[0030] Examples of products to which a herbal scent can be imparted by the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1a) 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.

[0031] The amount of the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1a) in the 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 the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1a) 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 1-ethylcyclohexanecarboxylic acid ester represented by formula (1a) is used as an aroma oil, perfume, or the like, the amount of the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1a) in the product may be 80% by mass or more, or even 100% by mass.

[0032] [Method for producing 1-ethylcyclohexanecarboxylic acid ester] There are no limitations on the method for producing the 1-ethylcyclohexanecarboxylic acid ester 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 mentioned above, the 1-ethylcyclohexanecarboxylic acid ester obtained by the production method shown below is also preferably used as a fragrance, and is also preferably used in the fragrance-adding method. The production method shown below is also included in the present invention.

[0033] The method for producing a 1-ethylcyclohexanecarboxylic acid ester of the present invention is a method for producing a 1-ethylcyclohexanecarboxylic acid ester, which comprises reacting a compound represented by the following general formula (2) with carbon monoxide and an alcohol represented by the following general formula (3) in the presence of hydrogen fluoride to obtain a 1-ethylcyclohexanecarboxylic acid ester represented by the following general formula (1): (In formula (2), one of the carbon-carbon bonds including the dashed line is a double bond and the others are single bonds. In formula (3), R 1 represents an alkyl group having 1 to 3 carbon atoms. 1 is R in formula (3) 1 and represents an alkyl group having 1 to 3 carbon atoms.)

[0034] <Compound Represented by Formula (2)> The compound represented by formula (2) is any one of a compound represented by formula (2a) below, a compound represented by formula (2b) below, and a compound represented by formula (2c) below, but is preferably at least one selected from the group consisting of a compound represented by formula (2a) below and a compound represented by formula (2b) below, and more preferably a compound represented by formula (2a) below. The compound represented by formula (2a) is 4-ethylcyclohexene, and the compound represented by formula (2b) is vinylcyclohexane. Therefore, the compound represented by formula (2) is preferably at least one selected from the group consisting of vinylcyclohexane and 4-ethylcyclohexene, and more preferably 4-ethylcyclohexene.

[0035] The compound represented by formula (2a) may be obtained by hydrogenating 4-vinylcyclohexene. That is, in the present production method, when the compound represented by formula (2) is 4-ethylcyclohexene, the method preferably includes a step of hydrogenating 4-vinylcyclohexene to obtain 4-ethylcyclohexene. The reaction formula is shown below.

[0036] The reaction conditions for the hydrogenation are not particularly limited, but may be those generally used for hydrogenating unsaturated bonds.

[0037] It is preferable to use a catalyst for hydrogenation. There are no particular limitations on the hydrogenation catalyst, but a catalyst containing at least one metal selected from Groups 8 to 11 of the periodic table is preferred. Specific examples include catalysts containing at least one metal selected from iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold. The hydrogenation catalyst may be a solid catalyst or a homogeneous catalyst, but a solid catalyst is preferred from the viewpoint of separability from the reactants.

[0038] Examples of solid catalysts include unsupported metal catalysts and supported metal catalysts. Preferred unsupported metal catalysts include Raney catalysts such as Raney nickel, Raney cobalt, and Raney copper, and oxides and colloidal catalysts of platinum, palladium, rhodium, ruthenium, and the like.

[0039] Examples of supported metal catalysts include those in which at least one of iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold is supported on or mixed with a carrier such as magnesia, zirconia, ceria, diatomaceous earth, activated carbon, alumina, silica, zeolite, or titania, and preferred are supported copper catalysts in which a copper catalyst such as a copper-chromium catalyst (Adkins catalyst), a copper-zinc catalyst, or a copper-iron catalyst is supported on a carrier, supported platinum catalysts such as Pt / C or Pt / alumina, supported palladium catalysts such as Pd / C or Pd / alumina, supported ruthenium catalysts such as Ru / C or Ru / alumina, and supported rhodium catalysts such as Rh / C or Rh / alumina. Of these, it is more preferable to use a copper-containing catalyst in terms of reaction activity and selectivity.

[0040] The amount of the hydrogenation catalyst used varies depending on the type of catalyst, but is suitably 0.001 to 100% by mass, preferably 0.01 to 30% by mass, and more preferably 0.1 to 20% by mass, based on the raw material 4-vinylcyclohexene.

[0041] The hydrogen pressure may be either normal pressure or elevated pressure, and is usually in the range of 0.1 to 4.0 MPa, preferably 0.1 to 3.0 MPa, and more preferably 0.1 to 2.0 MPa.

[0042] The hydrogenation reaction can be carried out without a solvent, but a solvent may be used. Examples of the solvent include esters such as ethyl acetate and butyl acetate, aromatic compounds such as benzene, o-dichlorobenzene, toluene, and xylene, hydrocarbons such as hexane, heptane, and cyclohexane, alcohols such as methanol, ethanol, isopropyl alcohol, t-butyl alcohol, ethylene glycol, and diethylene glycol, ethers such as dioxane, tetrahydrofuran, dimethoxyethane, and diglyme, and mixtures thereof.

[0043] The amount of the solvent used in the hydrogenation reaction is usually 0.1 to 30 times by mass, preferably 0.2 to 20 times by mass, relative to the amount of 4-vinylcyclohexene used as the raw material.

[0044] The reaction temperature for the hydrogenation reaction is usually from -90°C to 200°C, preferably from 20°C to 150°C, and more preferably from 20°C to 100°C.

[0045] The type of hydrogenation reaction is not particularly limited as long as it is capable of catalytic hydrogenation, and may be any commonly used known type, such as a suspended bed reactor in which a catalyst is fluidized with a fluid to carry out catalytic hydrogenation, or a fixed bed reactor in which a catalyst is packed and immobilized and a fluid is supplied to carry out catalytic hydrogenation.

[0046] <Alcohol represented by formula (3)> The alcohol represented by formula (3) is a monohydric alcohol having an alkyl group having 1 to 3 carbon atoms. 1 is an alkyl group having 1 to 3 carbon atoms, specifically, R 1is preferably at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, more preferably at least one selected from the group consisting of a methyl group and an ethyl group, and even more preferably an ethyl group. Specifically, the alcohol represented by formula (3) is preferably methanol, ethanol, 1-propanol, or 2-propanol, and more preferably ethanol.

[0047] <Carbonylation Reaction> In the production method of the present invention, a compound represented by formula (2) is reacted with carbon monoxide and an alcohol represented by formula (3) in the presence of hydrogen fluoride to obtain a 1-ethylcyclohexanecarboxylic acid ester represented by formula (1). First, carbonylation is carried out using carbon monoxide, and the resulting carbonyl compound is reacted with an alcohol to obtain a 1-ethylcyclohexanecarboxylic acid ester represented by formula (1). First, the carbonylation reaction will be described, and then the conversion to an ester will be described.

[0048] The hydrogen fluoride used in the carbonylation reaction is a solvent, a catalyst, and a secondary raw material for the reaction, and therefore is used in a substantially anhydrous form. The amount of hydrogen fluoride used is preferably 4 to 15 molar times, and more preferably 6 to 10 molar times, relative to the raw material compound represented by formula (2). When the molar ratio of hydrogen fluoride is 4 or more, the reaction proceeds efficiently, side reactions such as disproportionation and polymerization can be suppressed, and the target product, 1-ethylcyclohexanecarboxylic acid ester represented by formula (1), can be obtained in high yield. Furthermore, from the viewpoint of raw material costs and productivity, the molar ratio of hydrogen fluoride is preferably 15 or less.

[0049] The carbon monoxide used in the carbonylation reaction may contain an inert gas such as nitrogen or methane, but the carbon monoxide partial pressure during the reaction is preferably 0.5 to 5 MPa, more preferably 1 to 3 MPa. If the carbon monoxide partial pressure is higher than 0.5 MPa, the carbonylation reaction proceeds sufficiently, and side reactions such as disproportionation and polymerization do not occur concomitantly, making it possible to obtain the target product, 1-ethylcyclohexanecarboxylic acid ester represented by formula (1), in high yield. Furthermore, from the viewpoint of equipment load, it is preferable that the carbon monoxide partial pressure be 5 MPa or less.

[0050] There are no particular limitations on the type of carbonylation reaction, and any of batch, semi-continuous, and continuous methods may be used. The reaction temperature for the carbonylation reaction is preferably −50° C. to 30° C., more preferably −40° C. to 0° C., and even more preferably −50° C. to −25° C. A reaction temperature of 30° C. or lower will result in a good yield. From the standpoint of reaction rate, it is preferable to carry out the reaction at −50° C. or higher.

[0051] In the carbonylation reaction, an acid fluoride is produced from hydrogen fluoride and carbon monoxide. After excess hydrogen fluoride is removed from the produced acid fluoride reaction solution, it may be purified by a conventional method such as distillation before use, but it is preferable to react the acid fluoride directly with an alcohol to convert it into an ester.

[0052] <Conversion to Ester> As described above, when the reaction solution produced in the carbonylation reaction is reacted with an alcohol to synthesize an ester, the acid fluoride may be separated and then reacted again with the alcohol in the presence of a hydrogen fluoride catalyst. However, it is preferable to react the acid fluoride directly with the alcohol without separating it to obtain an ester. From the viewpoint of corrosiveness of the reaction apparatus, it is preferable to add a predetermined amount of alcohol to the acid fluoride reaction solution.

[0053] The amount of the alcohol represented by formula (3) used is preferably 0.5 to 2.0 times by mole, more preferably 0.8 to 1.5 times by mole, relative to the compound represented by formula (2) used as the raw material in the carbonylation step. A molar ratio of the alcohol of 0.5 times or more is preferred because the amount of unreacted fluoride remaining is small and corrosion of equipment in subsequent steps is small, while a molar ratio of 2.0 times or less is preferred from the viewpoint of suppressing corrosion of equipment due to suppression of dehydration reactions between alcohol molecules.

[0054] The reaction temperature of the acid fluoride and the alcohol is preferably 20° C. or less from the viewpoint of suppressing decomposition of the ester. A temperature of 20° C. or less is preferred because dehydration reactions between alcohol molecules can be suppressed.

[0055] After hydrogen fluoride is distilled off from the resulting ester, the resulting product is purified by a conventional method such as distillation to obtain a 1-ethylcyclohexanecarboxylic acid ester represented by formula (1). The resulting 1-ethylcyclohexanecarboxylic acid ester has an excellent herbal fragrance and can therefore be suitably used as a fragrance. By incorporating the 1-ethylcyclohexanecarboxylic acid ester as an active ingredient in a fragrance composition, a fragrance composition can be obtained that has a herbal feel and exhibits excellent fragrance diffusibility. Furthermore, this production method enables the efficient production of 1-ethylcyclohexanecarboxylic acid ester, thereby enabling the production of a fragrance that is industrially practical and yet has an excellent fragrance.

[0056] The present invention will be specifically described based on the following examples, but the present invention is not limited to these examples.

[0057] [Analysis and Evaluation] <Purity (GC Analysis)> The purity of the 1-ethylcyclohexanecarboxylic acid esters obtained in Examples 1 to 4 was determined by gas chromatography (GC analysis). The conditions for GC analysis are shown below. [GC Analysis Conditions] 100 mg of a sample (product of the Example) was diluted with 2 mL of diethyl ether (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The measurement device used was a "GC-6850" from Agilent Technologies, and the column used was a "DB-1 (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm)" from J&W. The temperature was raised from 80°C to 300°C at a rate of 10°C / min.

[0058] <Identification of Compounds (GC-MS Analysis, NMR Spectroscopic Analysis)> Gas chromatography mass spectrometry (GC-MS analysis) and NMR spectroscopic analysis were used to identify the 1-ethylcyclohexanecarboxylic acid esters obtained in Examples 1 to 4. The conditions for each analysis are shown below. [GC-MS Analysis Conditions] 10 mg of a sample (1-ethylcyclohexanecarboxylic acid ester) was diluted with 2 mL of diethyl ether (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The measurement equipment used was an Agilent Technologies 5977B GC / MSD, and the column used was a J&W HP-5 (inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm). The temperature was increased from 80°C to 300°C at a rate of 10°C / min. The ionization method for the MSD was EI. [NMR Spectroscopic Analysis Conditions] 10 mg of a sample (1-ethylcyclohexanecarboxylic acid ester) was diluted with 0.8 mL of chloroform-d (deuteration rate 99.8%, containing 0.05 vol% TMS, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and analyzed using an Agilent-NMR-vnmrs400 manufactured by Varian. １ H-NMR and １３ C-NMR was measured.

[0059] <Fragrance Evaluation> The 1-ethylcyclohexanecarboxylic acid esters obtained in the Examples and the fragrance compositions obtained in the Examples and Comparative Examples were subjected to a sensory evaluation using smell test papers. The sensory evaluation was carried out by four expert panelists with more than five years of evaluation experience.

[0060] [Synthesis of Raw Materials] Production Example 1 (Synthesis of 4-ethylcyclohexene) A 5 L stainless steel autoclave equipped with a magnetic induction stirrer, three inlet nozzles at the top, and one filter-equipped extraction nozzle at the bottom, and capable of controlling the internal temperature using a jacket, was charged with 2.0 g of Cu-Cr catalyst (manufactured by JGC Catalysts and Chemicals Co., Ltd., trade name "N-203S") and 100 g of heptane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; special grade), and activated for 1 hour at 170 ° C. and a hydrogen pressure of 2 MPa. After cooling, only heptane was extracted from the filter-equipped extraction nozzle at the bottom, and 50 g of 4-vinylcyclohexene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.25 g of heptane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; special grade) were charged, and the mixture was subjected to a hydrogenation reaction at 50 ° C. and a hydrogen pressure of 1 MPa with stirring for 5 hours. The reaction mixture was filtered to remove the catalyst, and the resulting reaction mixture was purified in a distillation column with 20 theoretical plates to obtain 45 g of 4-ethylcyclohexene.

[0061] [Production of 1-ethylcyclohexanecarboxylic acid ester] Example 1 (Production of ethyl 1-ethylcyclohexanecarboxylate) <Carbonylation step> An experiment was carried out using a 500 mL stainless steel autoclave equipped with a magnetic induction stirrer, three inlet nozzles at the top, and one withdrawal nozzle at the bottom, with the internal temperature controlled by a jacket. First, the atmosphere inside the autoclave was purged with nitrogen, and then 120 g (6 mol) of hydrogen fluoride was introduced. The liquid temperature was adjusted to -10°C, and the autoclave was then pressurized to 2 MPa with carbon monoxide. While maintaining the reaction temperature at -10°C and the reaction pressure at 2 MPa, a mixture of 67 g (0.6 mol) of 4-ethylcyclohexene obtained in Production Example 1 and 67 g of heptane was supplied from the top of the autoclave over 45 minutes to carry out the carbonylation reaction. After the supply was completed, stirring was continued for approximately 20 minutes until no carbon monoxide absorption was observed.

[0062] <Esterification Step> Subsequently, while maintaining the reaction temperature at -10°C, 41.7 g (0.9 mol) of ethanol was fed from the top of the autoclave over 15 minutes, and esterification was carried out with stirring for 1 hour. The reaction solution was extracted from the bottom of the autoclave into ice water, and the oil and aqueous phases were separated. The oil phase was washed once with 100 mL of 2% aqueous caustic soda solution and twice with 100 mL of distilled water, and then dehydrated with 10 g of anhydrous sodium sulfate. The resulting oil phase was purified in a distillation column with 20 theoretical plates, yielding 78 g of ethyl 1-ethylcyclohexanecarboxylate as a colorless, transparent liquid. The results of an aroma evaluation of the resulting ethyl 1-ethylcyclohexanecarboxylate are shown in Table 1.

[0063] [Ethyl 1-ethylcyclohexanecarboxylate] GC analysis showed that the purity of the main product was 99.7%. GC-MS analysis of the main product showed that the purity was 184 (10, M ＋ ), 156 (25), 129 (24), 111 (100), 69 (74), 55 (25), which were confirmed to match the molecular weight of the target compound, 184. １ H-NMR (CDCl ３ , 400 MHz, δ ppm) analytical values ​​were 0.81 (t, J = 7.6 Hz, 3H), 1.10-1.40 (m, 8H), 1.46-1.61 (m, 5H), 2.01-2.11 (m, 2H), 4.15 (q, J = 7.1 Hz, 2H), and １３ C-NMR (CDCl ３ , 400MHz, δppm) was analyzed as 8.5 (CH ３ ), 14.3 (CH ３ ), 23.3 (CH ２ ), 26.0 (CH ２ ), 33.3 (CH ２ ), 33.8 (CH ２ ), 47.2 (C), 59.9 (OCH ２ ), 176.8 (CO), and the main product was identified as ethyl 1-ethylcyclohexanecarboxylate.

[0064] Example 2 (Production of methyl 1-ethylcyclohexanecarboxylate) 72 g of methyl 1-ethylcyclohexanecarboxylate was obtained as a colorless, transparent liquid in the same manner as in Example 1, except that 41.7 g (0.9 mol) of ethanol used in the esterification step in Example 1 was changed to 27 g (0.84 mol) of methanol. The results of the odor evaluation of the obtained methyl 1-ethylcyclohexanecarboxylate are shown in Table 1.

[0065] [1-ethylcyclohexanemethyl carboxylate] GC analysis showed that the purity of the main product was 99.8%. GC-MS analysis of the main product showed that the purity was 170 (13, M ＋ ), 142 (25), 115 (44), 102 (20), 69 (100), 55 (37), which were confirmed to match the molecular weight of the target compound, 170. １ H-NMR (CDCl ３ , 400 MHz, δ ppm) analytical values ​​were 0.79 (t, J = 7.4 Hz, 3H), 1.12-1.38 (m, 5H), 1.47-1.62 (m, 5H), 2.01-2.12 (m, 2H), 3.68 (s, 3H), and １３ C-NMR (CDCl ３ , 400 MHz, δ ppm) was 8.6 (CH ３ ), 23.3 (CH ２ ), 26.0 (CH ２ ), 33.3 (CH ２ ), 33.8 (CH ２ ), 47.5(C), 51.4(OCH ３ ), 177.3 (CO), and the main product was identified as methyl 1-ethylcyclohexanecarboxylate.

[0066] Example 3 (Production of propyl 1-ethylcyclohexanecarboxylate) 78 g of propyl 1-ethylcyclohexanecarboxylate was obtained as a colorless, transparent liquid in the same manner as in Example 1, except that 41.7 g (0.9 mol) of ethanol used in the esterification step in Example 1 was changed to 49 g (0.82 mol) of 1-propanol. The results of the odor evaluation of the obtained propyl 1-ethylcyclohexanecarboxylate are shown in Table 1.

[0067] [1-ethylcyclohexanepropyl carboxylate] GC analysis showed that the purity of the main product was 98.7%. GC-MS analysis of the main product showed that the purity was 198 (5, M ＋ ), 170 (15), 157 (18), 143 (12), 111 (100), 101 (20), 69 (68), 55 (23), which were confirmed to match the molecular weight of the target compound, 198. １ H-NMR (CDCl ３ , 400 MHz, δ ppm) were analyzed to be 0.80 (t, J = 7.6 Hz, 3H), 0.95 (t, J = 7.4 Hz, 3H), 1.11-1.39 (m, 5H), 1.47-1.71 (m, 7H), 2.02-2.12 (m, 2H), 4.04 (t, J = 6.6 Hz, 2H); １３ C-NMR (CDCl ３ , 400MHz, δppm) was analyzed as 8.5 (CH ３ ), 10.6 (CH ３ ), 22.1 (CH ２ ), 23.3 (CH ２ ), 26.1 (CH ２ ), 33.3 (CH ２ ), 33.8 (CH ２ ), 47.4(C), 65.6(OCH ２ ), 176.9 (CO), and the main product was identified as propyl 1-ethylcyclohexanecarboxylate.

[0068] Example 4 (Production of isopropyl 1-ethylcyclohexanecarboxylate) 71 g of isopropyl 1-ethylcyclohexanecarboxylate was obtained as a colorless, transparent liquid in the same manner as in Example 1, except that 41.7 g (0.9 mol) of ethanol used in the esterification step in Example 1 was changed to 46 g (0.76 mol) of 2-propanol. The results of the odor evaluation of the obtained isopropyl 1-ethylcyclohexanecarboxylate are shown in Table 1.

[0069] [1-Ethylcyclohexanecarboxylic acid isopropyl] As a result of GC analysis, the purity of the main product was 99.9%. As a result of GC-MS analysis of the main product, it was found that the chromatogram was 198 (5, M ＋), 170 (15), 111 (100), 1013 (30), 69 (78), 55 (24), which were confirmed to match the molecular weight of the target substance, 198. １ H-NMR (CDCl ３ , 400 MHz, δ ppm) were analyzed to be 0.80 (t, J=7.6 Hz, 3H), 1.08-1.22 (m, 3H), 1.22 (d, J=6.0 Hz, 6H), 1.26-1.40 (m, 2H), 1.46-1.61 (m, 5H), 2.02-2.10 (m, 2H), 5.04 (dq, 1H, J=6.3 Hz, 6.3 Hz); １３ C-NMR (CDCl ３ , 400 MHz, δ ppm) was analyzed as 8.4 (CH ３ ), 21.9 (CH ３ ), 23.3 (CH ２ ), 23.3 (CH ２ ), 26.1 (CH ２ ), 33.4 (CH ２ ), 33.8 (CH ２ ), 47.0 (C), 66.9 (OCH ２ ), 176.2 (CO), and the major product was identified as isopropyl 1-ethylcyclohexanecarboxylate.

[0070]

[0071] It is clear that the 1-ethylcyclohexanecarboxylic acid esters obtained in Examples 1 to 4 have a herbal fragrance and are also diffusible, and therefore can be suitably used as fragrances. Furthermore, it is clear that the 1-ethylcyclohexanecarboxylic acid esters obtained in Examples 1 to 4 can be suitably used in fragrance-imparting methods that impart a herbal fragrance. In particular, it is clear that ethyl 1-ethylcyclohexanecarboxylate obtained in Example 1 has a fruity fragrance in addition to a herbal fragrance, and therefore can be suitably used as a fragrance.

[0072] Examples 5 to 8 and Comparative Example 1 (Fragrance Compositions) Floral-type fragrance compositions were prepared containing the 1-ethylcyclohexanecarboxylic acid esters obtained in Examples 1 to 4 as blending components. As a comparative example, a fragrance composition was prepared in which the 1-ethylcyclohexanecarboxylic acid ester was replaced with dipropylene glycol as a solvent. The composition of the floral-type fragrance composition is shown in Table 2. The results of the fragrance evaluation of the floral-type fragrance composition are shown in Table 3.

[0073]

[0074] 1) Triplal: IFF (trade name), compound name: 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde 2) Magnol: Kao Corporation (trade name), mixture mainly composed of ethylnorbornylcyclohexanol 3) Undecavertol: Givaudan (trade name), compound name: 4-methyl-3-decen-5-ol 4) Poirenate: Kao Corporation (registered trademark), compound name: ethyl 2-cyclohexylpropionate 5) Fultate: Kao Corporation (registered trademark), compound name: ethyltricyclo[5.2.1.0] 2,6 ] decane-2-carboxylate 6) Lilial: Givaudan (trade name), compound name: p-tert-butyl-α-methylhydrocinnamic aldehyde 7) Ambercore: Kao Corporation (registered trademark), compound name: 1-(2-tert-butylcyclohexyloxy)-2-butanol 8) 50% IPM: 50% isopropyl myristate (IPM) solution 9) Ambroxan: Kao Corporation (registered trademark), compound name: dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan 10) 5% DPG: 5% dipropylene glycol (DPG) solution

[0075]

[0076] Example 9 and Comparative Example 2 (Fragrance Composition) A fragrance composition with a sweet pea scent was prepared, containing the ethyl 1-ethylcyclohexanecarboxylate obtained in Example 1 as a blending component. As a comparative example, a fragrance composition was prepared in which the 1-ethylcyclohexanecarboxylic acid ester was replaced with dipropylene glycol as a solvent. The composition of the fragrance composition with a sweet pea scent is shown in Table 4. The results of the fragrance evaluation of the fragrance composition with a sweet pea scent are shown in Table 5.

[0077]

[0078]

[0079] Example 10 and Comparative Example 3 (Fragrance Composition) A peach-type fragrance composition was prepared containing the ethyl 1-ethylcyclohexanecarboxylate obtained in Example 1 as a blending component. As a comparative example, a fragrance composition was prepared in which the 1-ethylcyclohexanecarboxylic acid ester was replaced with dipropylene glycol as a solvent. The composition of the peach-type fragrance composition is shown in Table 6. The results of the fragrance evaluation of the peach-type fragrance composition are shown in Table 7.

[0080]

[0081]

[0082] The fragrance compositions of the Examples had a herbal feel and improved fragrance diffusibility compared to the fragrance compositions of the Comparative Examples. As shown in Tables 3, 5, and 7, the fragrance compositions of the Examples have excellent fragrance characteristics with excellent diffusibility, and are therefore useful as fragrance components for a wide range of toiletry products, particularly laundry cleansers and body cleansers. In particular, fragrance compositions containing ethyl 1-ethylcyclohexanecarboxylate as an active ingredient are extremely useful as fragrance components because they also have a fruity feel with excellent diffusibility, as shown in Examples 5 and 10.

[0083] From the above results, it can be seen that the fragrance compositions of the Examples have a herbal feel and are excellent in fragrance diffusibility. It can also be seen that the specific 1-ethylcyclohexanecarboxylic acid esters used in the Examples have a herbal fragrance and can further impart fragrance diffusibility, and therefore can be used as fragrances. It can also be seen that the specific 1-ethylcyclohexanecarboxylic acid esters used in the Examples can be suitably used in fragrance-imparting methods that impart a herbal fragrance.

Claims

1. A fragrance composition containing, as an active ingredient, a 1-ethylcyclohexanecarboxylic acid ester represented by the following general formula (1): 【Chemical 1】 (In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms.)

2. The fragrance composition according to claim 1, further comprising a fragrance substance other than the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1).

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

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

5. R 1 The fragrance composition according to any one of claims 1 to 3, wherein is an ethyl group.

6. Use of 1-ethylcyclohexanecarboxylic acid ester represented by the following general formula (1) as a fragrance: 【Chemistry 2】 (In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms.)

7. R 1 The use according to claim 6, wherein is at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

8. The use according to claim 6, wherein the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1) imparts a herbal scent.

9. R 1 The use according to any one of claims 6 to 8, wherein is an ethyl group.

10. The use according to claim 9, wherein the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1) imparts a herbal scent and a fruity scent.

11. A method for imparting a herbal fragrance using a 1-ethylcyclohexanecarboxylic acid ester represented by the following formula (1a): 【Chemistry 3】 (In formula (1a), R 2 represents at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

12. R 2 is an ethyl group, and the 1-ethylcyclohexanecarboxylic acid ester represented by formula (1a) imparts a herbal scent and a fruity scent.

13. A method for producing a 1-ethylcyclohexanecarboxylic acid ester, comprising reacting a compound represented by the following general formula (2) with carbon monoxide and an alcohol represented by the following general formula (3) in the presence of hydrogen fluoride to obtain a 1-ethylcyclohexanecarboxylic acid ester represented by the following general formula (1): 【Chemistry 4】 (In formula (2), one of the carbon-carbon bonds including the dashed line is a double bond and the others are single bonds. In formula (3), R 1 represents an alkyl group having 1 to 3 carbon atoms. 1 is R in formula (3) 1 and represents an alkyl group having 1 to 3 carbon atoms.)

14. R 1 is at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

15. R 1 The method for producing 1-ethylcyclohexanecarboxylic acid ester according to claim 13, wherein is an ethyl group.

16. The method for producing a 1-ethylcyclohexanecarboxylic acid ester according to any one of claims 13 to 15, wherein the compound represented by general formula (2) is at least one selected from the group consisting of vinylcyclohexane and 4-ethylcyclohexene.

17. The method for producing a 1-ethylcyclohexanecarboxylic acid ester according to any one of claims 13 to 15, comprising a step of hydrogenating 4-vinylcyclohexene to obtain 4-ethylcyclohexene, wherein the compound represented by general formula (2) is 4-ethylcyclohexene.

Images