Fragrance composition and method for producing 1-ethylcyclohexane formate

Abstract

The present invention is: a fragrance composition containing, as an active ingredient, a 1-ethylcyclohexane formic acid ester represented by general formula (1); the use of a 1-ethylcyclohexane formic acid ester as a fragrance; and a method for producing a 1-ethylcyclohexane formic acid ester. The perfume composition contains, as an active ingredient, 1-ethylcyclohexane formic acid ester which can impart a herbal aroma and further impart diffusivity of the aroma, thereby having a herbal feeling and excellent diffusivity of the aroma. (In formula (1), R1 represents an alkyl group having 1-3 carbon atoms. ). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a fragrance composition and a method for producing 1-ethylcyclohexanecarboxylate. Background Art

[0002] Ester compounds are widely used as fragrances. In particular, formates and acetates are widely found in nature, and most have a fruity aroma. Synthetic fragrances that are ester compounds are also known.

[0003] For example, Non-Patent Document 1 describes that methyl 1-methyl-3-cyclohexenecarboxylate has a complex aroma similar to chrysanthemum or thujone and is used as a fragrance.

[0004] Prior art literature

[0005] Non-patent literature

[0006] Non-patent document 1: Indo Motoichi, "Supplementary and Revised Edition of Synthetic Fragrance Chemistry and Product Knowledge," 1996, p. 672, Chemical Industry Daily Summary of the Invention

[0007] Problems to be solved by the invention

[0008] As mentioned above, many ester compounds are used as natural or synthetic fragrances. However, in order to enhance the value of fragrances, cosmetics, detergents, sanitary products, sundry goods, pharmaceuticals, foods, and other products, new fragrances are needed. Typically, fragrances are used as blended fragrances, which are a mixture of multiple fragrances. There is a particular demand for fragrance ingredients that exhibit excellent effects when mixed with other fragrances.

[0009] Furthermore, since flavor is affected by impurities generated during the production process, a method for producing a fragrance having both industrial applicability and excellent flavor is also desired.

[0010] The present invention aims to provide a fragrance composition having novel fragrance and properties, and the use of a compound capable of imparting novel fragrance and properties to a fragrance composition, a method for imparting fragrance, and a method for producing the compound.

[0011] Solutions for solving problems

[0012] The present inventors have discovered that a fragrance composition having novel fragrance and properties by containing a specific ester compound as an active ingredient, that the ester compound is excellent as a fragrance, and that there is an efficient method for producing the ester compound, thereby completing the present invention.

[0013] That is, the present invention is as follows.

[0014] [1] A fragrance composition comprising 1-ethylcyclohexanecarboxylate represented by the following general formula (1) as an active ingredient.

[0015]

[0016] (In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms.)

[0017] [2] The fragrance composition according to [1], further comprising a fragrance substance other than 1-ethylcyclohexanecarboxylate represented by formula (1).

[0018] [3] The fragrance composition according to [2], wherein the fragrance substance other than 1-ethylcyclohexanecarboxylate 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 1-ethylcyclohexanecarboxylate represented by formula (1).

[0019] [4] The flavor composition according to any one of [1] to [3], wherein R 1 It is at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

[0020] [5] The flavor composition according to any one of [1] to [4], wherein R 1 For ethyl.

[0021] [6] Use of 1-ethylcyclohexanecarboxylate represented by the following general formula (1) as a fragrance.

[0022]

[0023] (In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms.)

[0024] [7] The application according to [6], wherein R 1 It is at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

[0025] [8] The use according to [6] or [7], wherein the 1-ethylcyclohexanecarboxylate represented by formula (1) imparts a herbal aroma.

[0026] [9] The use according to any one of the above [6] to [8], wherein R 1 For ethyl.

[0027]

[10] The use according to [9], wherein the 1-ethylcyclohexanecarboxylate represented by formula (1) imparts herbal and fruity aromas.

[0028]

[11] A method for imparting aroma, comprising imparting herbal aroma using 1-ethylcyclohexanecarboxylate represented by the following formula (1a).

[0029]

[0030] (In formula (1a), R 2 represents at least one selected from the group consisting of methyl, ethyl, n-propyl and isopropyl.)

[0031]

[12] The method for imparting fragrance according to

[11] , wherein R 2 The 1-ethylcyclohexanecarboxylate represented by the above formula (1a) is an ethyl group and imparts herbal and fruity aromas.

[0032]

[13] A method for producing 1-ethylcyclohexanecarboxylate, wherein carbon monoxide and an alcohol represented by the following general formula (3) are reacted with a compound represented by the following general formula (2) in the presence of hydrogen fluoride to obtain 1-ethylcyclohexanecarboxylate represented by the following general formula (1).

[0033]

[0034] (In formula (2), one position of the carbon-carbon bond including the dotted 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. In formula (1), R 1 R in formula (3) 1 Same as , represents an alkyl group with 1 to 3 carbon atoms.)

[0035]

[14] The method for producing 1-ethylcyclohexanecarboxylate according to

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

[0036]

[15] The method for producing 1-ethylcyclohexanecarboxylate according to

[13] or

[14] , wherein R 1 For ethyl.

[0037]

[16] The method for producing 1-ethylcyclohexanecarboxylate according to any one of

[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.

[0038]

[17] The method for producing 1-ethylcyclohexanecarboxylate according to any one of

[13] to

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

[0039] Effects of the Invention

[0040] According to the present invention, there are provided a fragrance composition having a herbal aroma and excellent fragrance diffusibility by containing 1-ethylcyclohexanecarboxylate as an active ingredient, the fragrance composition having a herbal aroma and excellent fragrance diffusibility, the use of 1-ethylcyclohexanecarboxylate as a fragrance, and a method for producing 1-ethylcyclohexanecarboxylate. DETAILED DESCRIPTION

[0041] Hereinafter, in this specification, the description of "XX to YY" means "XX or more and YY or less".

[0042] [Fragrance composition]

[0043] The fragrance composition of the present invention contains 1-ethylcyclohexanecarboxylic acid ester represented by the following general formula (1) as an active ingredient.

[0044]

[0045] (In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms.)

[0046] The fragrance composition of the present invention contains 1-ethylcyclohexanecarboxylate as an active ingredient, which imparts a herbal aroma and further enhances aroma diffusivity. Thus, the fragrance composition has a herbal feel and excellent aroma diffusivity, making it useful as a fragrance component for various products.

[0047] <1-Ethylcyclohexanecarboxylate>

[0048] In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms. Specifically, R 1 It 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 still more preferably an ethyl group.

[0049] R 1 In the case of an ethyl group, it has a fruity aroma in addition to a herbal aroma, and is therefore very useful as an active ingredient in a fragrance composition.

[0050] The 1-ethylcyclohexanecarboxylic acid ester represented by the above formula (1) is useful as an active ingredient of a fragrance composition. It has a herbal aroma and can impart a herbal aroma to the fragrance composition, and further, can impart fragrance diffusivity.

[0051] R 1 When it is a methyl group, it has a particularly good herbal aroma that diffuses well.

[0052] R 1 When it is ethyl, it has a herbal aroma and a fruity aroma that are particularly well diffused.

[0053] R 1 When it is n-propyl, it has a particularly good herbal aroma with good diffusion.

[0054] R 1 In the case of isopropyl, it has a particularly good herbal aroma with good diffusion.

[0055] The content of the 1-ethylcyclohexanecarboxylate in the fragrance composition of the present invention can be appropriately adjusted depending on the type of fragrance composition, the type of target aroma, the intensity of the aroma, etc., 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, even more preferably 0.1 to 10% by mass, even more preferably 0.5 to 10% by mass, and even more preferably 0.8 to 7% by mass.

[0056] <Other ingredients and usable products>

[0057] Examples of other ingredients other than the 1-ethylcyclohexanecarboxylate contained in the fragrance composition containing the 1-ethylcyclohexanecarboxylate include fragrance substances other than the 1-ethylcyclohexanecarboxylate represented by formula (1), surfactants, solvents, antioxidants, and colorants. Preferably, the fragrance composition is at least one selected from the group consisting of fragrance substances other than the 1-ethylcyclohexanecarboxylate represented by formula (1), surfactants, solvents, antioxidants, and colorants. More preferably, the fragrance composition is at least one selected from the group consisting of fragrance substances other than the 1-ethylcyclohexanecarboxylate represented by formula (1) and solvents. Furthermore, the fragrance substance other than the 1-ethylcyclohexanecarboxylate represented by formula (1) is more preferably present. That is, a preferred fragrance composition of the present invention contains the 1-ethylcyclohexanecarboxylate represented by formula (1) as an active ingredient and contains a fragrance substance other than the 1-ethylcyclohexanecarboxylate represented by formula (1).

[0058] By containing a fragrance substance other than 1-ethylcyclohexanecarboxylate represented by formula (1), the fragrance can be adjusted according to the target product. In addition, by containing a solvent, the fragrance can be easily dissolved and impregnated into the target product, and the intensity and duration of the fragrance can be adjusted.

[0059] Among them, it is preferred that the floral fragrance composition be composed of fragrance substances other than 1-ethylcyclohexanecarboxylate represented by formula (1), and 1-ethylcyclohexanecarboxylate represented by formula (1) be contained as an active ingredient in the floral fragrance composition.

[0060] The fragrance substances other than 1-ethylcyclohexanecarboxylate represented by formula (1) are not particularly limited as long as they are conventionally known fragrance components, and a wide range of fragrances can be used. For example, the following substances can be used alone, or two or more of the following substances can be selected and used in any mixing ratio.

[0061] The fragrance substance other than 1-ethylcyclohexanecarboxylate 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 1-ethylcyclohexanecarboxylate represented by formula (1). It is more preferably at least one selected from the group consisting of alcohols, aldehydes, and esters other than 1-ethylcyclohexanecarboxylate represented by formula (1). It is further preferably at least one selected from the group consisting of alcohols and aldehydes.

[0062] Examples of the hydrocarbons include limonene, α-pinene, β-pinene, terpenes, cedarene, longifolene, and valencene.

[0063] Examples of the alcohols include linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenol, ethyl linalool, farnesol, nerolidol, cis-3-hexenol, cedarol, menthol, borneol, β-phenylethanol, benzyl alcohol, phenylhexanol, 2,2,6-trimethylcyclohexyl-3-hexanol, 1-(2-tert-butylcyclohexyloxy)-2-butanol, 4-isopropylcyclohexanemethanol, 4- Tert-butyl cyclohexanol, 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, isobornyl cyclohexanol, 3,7-dimethyl-7-methoxyoctan-2-ol, etc.

[0064] Examples of the phenols include eugenol, thymol, and vanillin.

[0065] Examples of the esters include linalyl formate, citronellyl formate, geranyl formate, n-hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, terpineol acetate, nopylacetate acetate, bornyl acetate, isobornyl acetate, o-tert-butylcyclohexyl acetate, p-tert-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styraxyl acetate, cinnamyl acetate, dimethylbenzyl acetate, 3-pentyltetrahydropyran-4-yl acetate, citronellyl propionate, propionic acid, Tricyclodecenyl ester, allyl cyclohexyl propionate, ethyl 2-cyclohexyl propionate, benzyl propionate, citronellyl butyrate, dimethylbenzyl butyrate, tricyclodecenyl isobutyrate, methyl 2-nonanoate, 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, fruity esters, etc.

[0066] Examples of the aldehydes include n-octanal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecanal, citronellal, citral, hydroxycitronellal, dimethyltetrahydrobenzaldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, 2-cyclohexylpropionaldehyde, p-tert-butyl-α-methylhydrocinnamaldehyde, p-tert-butyl hydrocinnamaldehyde, p-isopropyl-α-methylhydrocinnamaldehyde, p-ethyl-α,α-dimethylhydrocinnamaldehyde, α-amylcinnamaldehyde, α-hexylcinnamaldehyde, piperonal, and α-methyl-3,4-methylenedioxyhydrocinnamaldehyde.

[0067] Examples of the ketones include methyl heptenone, 4-methylene-3,5,6,6-tetramethyl-2-heptanone, pentylcyclopentanone, 3-methyl-2-(cis-2-penten-1-yl)-2-cyclopenten-1-one, methylcyclopentanolone, rhodone, γ-methylionone, α-ionone, carvone, menthone, camphor, nootkatone, benzylacetone, anisylacetone, methyl β-naphthone, 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, musk ketone, civetone, cyclopentadecanone, and cyclohexadecanone.

[0068] Examples of the acetals and ketals include acetaldehyde ethylphenylpropyl acetal, citral diethyl acetal, phenylacetaldehyde glycerol acetal, and ethyl acetoacetate ethylene glycol ketal.

[0069] Examples of the ethers include anethole, β-naphthyl methyl ether, β-naphthyl ethyl ether, limonene oxide, rose oxide, 1,8-cineole, racemic forms, and optically active dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan.

[0070] Examples of the nitriles include citronellyl nitrile and the like.

[0071] Examples of the lactones include γ-nonalactone, γ-undecanolactone, σ-dodecanolactone, γ-jasminelactone, coumarin, cyclopentadecanolide, cyclohexadecanolactone, ambrillolactone, ethylene glycol brassate, and 11-oxahexadecanolide.

[0072] 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, fennel, cloves, ginger, nutmeg, cardamom, cedar, cypress, sandalwood, vetiver, patchouli, and labdanum.

[0073] Examples of the solvent include dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, and triethyl citrate.

[0074] Examples of the surfactant include polyoxyethylene lauryl sulfate ether and the like.

[0075] The fragrance composition containing 1-ethylcyclohexanecarboxylic acid ester represented by the above general formula (1) can be used as a fragrance component of various products.

[0076] Examples of products that can use fragrance compositions include perfumes, colognes, and other fragrance products; shampoos, conditioners, hair conditioners, hair creams, mousses, gels, pomades, sprays, and other hair cosmetics; skin cosmetics such as lotions, serums, creams, emulsions, facial masks, foundations, powders, lipsticks, and various makeup products; dishwashing detergents, laundry detergents, softeners, disinfecting cleaners, deodorizing cleaners, room fragrances, furniture care products, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaching agents, fungicides, repellents, and various other health and hygiene cleaners; quasi-drugs such as dentifrices, mouthwashes, body washes, antiperspirants, and perming solutions; sundry goods such as toilet paper and paper towels; pharmaceuticals; and food. Among these, the fragrance composition containing 1-ethylcyclohexanecarboxylic acid ester represented by the general formula (1) is preferably used in toiletries such as laundry detergents and body detergents.

[0077] The amount of the fragrance composition blended into the above-mentioned product is not particularly limited and can be selected based on the type, properties, and sensory effects of the product to be scented. For example, the amount of the fragrance composition blended into the product is preferably 0.00001% by mass or greater, more preferably 0.0001% by mass or greater, and even more preferably 0.001% by mass or greater. Furthermore, it is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less.

[0078] In addition, when the fragrance composition is used as a fragrance oil, perfume, etc., the blending amount of the fragrance composition in the product may be 80% by mass or more, and may be 100% by mass.

[0079] [Application as fragrance]

[0080] 1-Ethylcyclohexanecarboxylate represented by the following general formula (1) has an excellent herbal aroma and can be used as a fragrance. The use of 1-ethylcyclohexanecarboxylate represented by the following general formula (1) as a fragrance is also included in the present invention.

[0081]

[0082] (In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms.)

[0083] In formula (1), R 1 represents an alkyl group having 1 to 3 carbon atoms. Specifically, R 1 It 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 still more preferably an ethyl group.

[0084] R 1 When it is an ethyl group, it has a fruity aroma in addition to a herbal aroma, and can therefore be used more suitably as a fragrance.

[0085] The 1-ethylcyclohexanecarboxylate represented by the above formula (1) has an excellent herbal aroma. Therefore, the use of the 1-ethylcyclohexanecarboxylate represented by the formula (1) imparts a herbal aroma. 1 If it is ethyl, it has a fruity aroma in addition to the herbal aroma, so R 1 In the case of an ethyl group, the use of 1-ethylcyclohexanecarboxylate represented by formula (1) imparts herbal and fruity aromas.

[0086] R 1 When it is a methyl group, it has a particularly good herbal aroma that diffuses well.

[0087] R 1When it is ethyl, it has a particularly good herbal and fruity aroma.

[0088] R 1 When it is n-propyl, it has a particularly good herbal aroma with good diffusion.

[0089] R 1 In the case of isopropyl, it has a particularly good herbal aroma with good diffusion.

[0090] 1-Ethylcyclohexanecarboxylate represented by formula (1) can be used as a fragrance component of various products. When 1-ethylcyclohexanecarboxylate represented by formula (1) is used as a fragrance component of various products, it can also be used as a component of the aforementioned fragrance composition.

[0091] Products in which 1-ethylcyclohexanecarboxylate represented by formula (1) can be used include, for example, fragrance products such as perfumes and colognes; shampoos, conditioners, hair conditioners, hair creams, mousses, gels, pomades, sprays and other hair cosmetics; skin cosmetics such as lotions, beauty serums, creams, emulsions, facial masks, foundations, powders, lipsticks and various makeup products; dishwashing detergents, laundry detergents, softeners, disinfecting cleaners, deodorizing cleaners, room fragrances, furniture care products, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaching agents, fungicides, repellents and various other health and hygiene cleaners; quasi-drugs such as dentifrices, mouthwashes, bath preparations, antiperspirants and perming solutions; sundry goods such as toilet paper and paper towels; pharmaceuticals; and food.

[0092] The amount of 1-ethylcyclohexanecarboxylate represented by formula (1) blended into the above-mentioned product is not particularly limited, and the blending amount of 1-ethylcyclohexanecarboxylate represented by formula (1) can be selected based on the type, properties, and sensory effects of the product to be perfumed. For example, the blending amount of 1-ethylcyclohexanecarboxylate 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. Furthermore, it is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less.

[0093] When 1-ethylcyclohexanecarboxylate represented by formula (1) is used as a fragrance oil, perfume, or the like, the amount of 1-ethylcyclohexanecarboxylate represented by formula (1) in the product may be 80% by mass or more, or may be 100% by mass.

[0094] [Fragrance method]

[0095] 1-Ethylcyclohexanecarboxylate represented by the following general formula (1a) has an excellent herbal aroma and can therefore impart herbal aroma to various products. The present invention also encompasses a method for imparting herbal aroma using 1-ethylcyclohexanecarboxylate represented by the following general formula (1a).

[0096] As a method for imparting a herbal aroma to a product, when the product is solid, coating, spraying, dipping, etc. can be used, and when the product is liquid, mixing can be used. It should be noted that when the herbal aroma is imparted by 1-ethylcyclohexanecarboxylate represented by formula (1a), 1-ethylcyclohexanecarboxylate represented by formula (1a) can also be used as a component of the aforementioned fragrance composition to impart a herbal aroma to various products.

[0097]

[0098] (In formula (1a), R 2 represents at least one selected from the group consisting of methyl, ethyl, n-propyl and isopropyl.)

[0099] In formula (1a), R 1 It is 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 still more preferably an ethyl group.

[0100] R 1 When it is an ethyl group, it has a fruity aroma in addition to a herbal aroma, and thus can impart herbal and fruity aromas to various products.

[0101] 1-Ethylcyclohexanecarboxylate represented by the above formula (1a) has an excellent herbal aroma and can therefore impart herbal aroma to various products. 1 If it is ethyl, it has a fruity aroma in addition to the herbal aroma, so R 1 In the case of an ethyl group, 1-ethylcyclohexanecarboxylate represented by formula (1a) can impart herbal aroma and fruity aroma to various products.

[0102] R 1 When it is a methyl group, it has a herbal aroma with good diffusibility, and imparts a herbal aroma to the product.

[0103] R 1 When it is ethyl, it has a herbal aroma and a fruity aroma with good diffusibility, and imparts a herbal aroma and a fruity aroma to the product.

[0104] R 1 When it is n-propyl, it has a particularly good herbal aroma with good diffusibility, and imparts a herbal aroma to the product.

[0105] R 1When it is an isopropyl group, it has a particularly good herbal aroma that diffuses well, and imparts a herbal aroma to the product.

[0106] Examples of products to which a herbal aroma can be imparted by the 1-ethylcyclohexanecarboxylate represented by formula (1a) include fragrance products such as perfumes and colognes; shampoos, conditioners, hair conditioners, hair creams, mousses, gels, pomades, sprays, and other hair cosmetics; skin cosmetics such as lotions, serums, creams, emulsions, facial masks, foundations, powders, lipsticks, and various makeup products; dishwashing detergents, laundry detergents, softeners, disinfecting cleaners, deodorizing cleaners, room fragrances, furniture care products, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaching agents, fungicides, repellents, and various other health and hygiene cleaners; quasi-drugs such as dentifrices, mouthwashes, body washes, antiperspirants, and perming solutions; sundry goods such as toilet paper and paper towels; pharmaceuticals; and foods.

[0107] The amount of 1-ethylcyclohexanecarboxylate represented by formula (1a) blended into the above-mentioned product is not particularly limited, and the blending amount of 1-ethylcyclohexanecarboxylate represented by formula (1a) can be selected based on the type, properties, and sensory effects of the product to be perfumed. For example, the blending amount of 1-ethylcyclohexanecarboxylate 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. Furthermore, it is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less.

[0108] When 1-ethylcyclohexanecarboxylate represented by formula (1a) is used as a fragrance oil, perfume, or the like, the amount of 1-ethylcyclohexanecarboxylate represented by formula (1a) in the product may be 80% by mass or more, or may be 100% by mass.

[0109] [Method for producing 1-ethylcyclohexanecarboxylate]

[0110] The production method of 1-ethylcyclohexanecarboxylate contained as an active ingredient in the fragrance composition of the present invention is not limited, but is preferably obtained by the production method described below. It should be noted that 1-ethylcyclohexanecarboxylate obtained by the production method described below is also preferably used as a fragrance, as described above, and is also preferably used in the aforementioned fragrance-imparting method. Furthermore, the production method described below is also encompassed by the present invention.

[0111] The method for producing 1-ethylcyclohexanecarboxylate of the present invention is a method for producing 1-ethylcyclohexanecarboxylate, comprising reacting carbon monoxide, an alcohol represented by the following general formula (3), and a compound represented by the following general formula (2) in the presence of hydrogen fluoride to obtain 1-ethylcyclohexanecarboxylate represented by the following general formula (1).

[0112]

[0113] (In formula (2), one position of the carbon-carbon bond including the dotted 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. In formula (1), R 1 R in formula (3) 1 Same as , represents an alkyl group with 1 to 3 carbon atoms.)

[0114] <Compound represented by formula (2)>

[0115] The compound represented by formula (2) is any one of the compound represented by formula (2a) below, the compound represented by formula (2b) below, and the compound represented by formula (2c) below, preferably at least one selected from the group consisting of the compound represented by formula (2a) below and the compound represented by formula (2b) below, and more preferably the compound represented by formula (2a) below.

[0116] 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.

[0117]

[0118] The compound represented by formula (2a) can also be obtained by hydrogenating 4-vinylcyclohexene. That is, in this production method, it is preferred that, when the compound represented by formula (2) is 4-ethylcyclohexene, the step of hydrogenating 4-vinylcyclohexene to obtain 4-ethylcyclohexene is provided. The reaction formula is shown below.

[0119]

[0120] The reaction conditions for the hydrogenation are not particularly limited, and the hydrogenation may be carried out under the reaction conditions generally used for hydrogenation of unsaturated bonds.

[0121] The hydrogenation is preferably carried out using a catalyst. The hydrogenation catalyst is not particularly limited as long as it is a catalyst, but preferably contains at least one metal selected from Groups 8 to 11 of the Periodic Table.

[0122] Specifically, catalysts containing at least one of iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold can be cited.

[0123] The hydrogenation catalyst may be a solid catalyst or a homogeneous catalyst, but a solid catalyst is preferred from the viewpoint of separation from the reaction product.

[0124] Examples of the solid catalyst include unsupported metal catalysts and supported metal catalysts. Preferred unsupported metal catalysts include Raney catalysts such as Raney nickel, Raney cobalt, and Raney copper, oxides of platinum, palladium, rhodium, and ruthenium, and colloidal catalysts.

[0125] Examples of supported metal catalysts include catalysts in which at least one of iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, and gold is supported or mixed on a carrier such as magnesium oxide, zirconium oxide, ceria, diatomaceous earth, activated carbon, alumina, silica, zeolite, and titanium dioxide. 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 and Pt / alumina; supported palladium catalysts such as Pd / C and Pd / alumina; supported ruthenium catalysts such as Ru / C and Ru / alumina; supported rhodium catalysts such as Rh / C and Rh / alumina; and the like. Among these, catalysts containing copper are more preferably used from the aspects of reaction activity and selectivity.

[0126] The amount of the hydrogenation catalyst used varies depending on the type of the catalyst, but is preferably 0.001 to 100% by mass, preferably 0.01 to 30% by mass, and more preferably 0.1 to 20% by mass relative to the raw material 4-vinylcyclohexene.

[0127] The hydrogen pressure may be either normal pressure or pressurized pressure, and is generally 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.

[0128] The hydrogenation reaction can be carried out in the absence of a solvent, but a solvent may also 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, isopropanol, tert-butanol, ethylene glycol, and diethylene glycol, ethers such as dioxane, tetrahydrofuran, dimethoxyethane, and diglyme, and mixtures thereof.

[0129] The amount of the solvent used in the hydrogenation reaction is usually 0.1 to 30 times by mass, and preferably 0.2 to 20 times by mass, based on the amount of 4-vinylcyclohexene as a raw material.

[0130] The reaction temperature of the hydrogenation reaction is usually -90°C to 200°C, preferably 20°C to 150°C, and more preferably 20°C to 100°C.

[0131] The form of the hydrogenation reaction is not particularly limited as long as it can carry out the catalytic hydrogenation reaction, and can be a commonly used known form. For example, a suspended bed reactor in which the catalyst is fluidized with a fluid to carry out the catalytic hydrogenation reaction, a fixed bed reactor in which the catalyst is filled and fixed and the fluid is supplied to carry out the catalytic hydrogenation reaction, etc. can be listed.

[0132] <Alcohol represented by formula (3)>

[0133] 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 1 The alcohol represented by formula (3) 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. Specifically, the alcohol represented by formula (3) is preferably methanol, ethanol, 1-propanol, or 2-propanol, and more preferably ethanol.

[0134] <Carbonylation reaction>

[0135] The production method of the present invention is to react carbon monoxide, an alcohol represented by formula (3), and a compound represented by formula (2) in the presence of hydrogen fluoride to obtain 1-ethylcyclohexanecarboxylate represented by formula (1). First, carbonylation is carried out using carbon monoxide, and the obtained carbonyl compound reacts with the alcohol to obtain 1-ethylcyclohexanecarboxylate represented by formula (1).

[0136] First, the carbonylation reaction will be described, and then the conversion to ester will be described.

[0137] The hydrogen fluoride used in the carbonylation reaction is a solvent for the reaction, a catalyst, and a by-raw material, so it is substantially anhydrous. The amount of hydrogen fluoride used is preferably 4 to 15 times by mole relative to the compound represented by formula (2) as the raw material, and more preferably 6 to 10 times by mole. If the molar ratio of hydrogen fluoride is 4 times by mole or more, the reaction proceeds efficiently, side reactions such as disproportionation and polymerization can be suppressed, and 1-ethylcyclohexanecarboxylate represented by formula (1) as the target product can be obtained in high yield. In addition, from the viewpoint of raw material cost and productivity, the molar ratio of hydrogen fluoride is preferably 15 times by mole or less.

[0138] The carbon monoxide used in the carbonylation reaction may also contain inert gases such as nitrogen and methane. 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 fully without the occurrence of side reactions such as disproportionation and polymerization, and 1-ethylcyclohexanecarboxylate represented by formula (1) as the target product can be obtained in high yield. In addition, from the perspective of equipment load, the carbon monoxide partial pressure is preferably 5 MPa or less.

[0139] The form of the carbonylation reaction is not particularly limited, and any method such as a batch method, a semi-continuous method, or a continuous method may be used.

[0140] The reaction temperature of 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 carbonylation reaction temperature of 30°C or lower provides a good yield. From the perspective of reaction rate, the reaction is preferably carried out at -50°C or higher.

[0141] In the carbonylation reaction, acyl fluoride is generated from hydrogen fluoride and carbon monoxide. The generated acyl fluoride reaction solution can be purified by conventional methods such as distillation after removing excess hydrogen fluoride, but is preferably directly reacted with an alcohol to convert it into an ester.

[0142] <Conversion to ester>

[0143] As described above, when the reaction solution generated in the carbonylation reaction is reacted with an alcohol to synthesize an ester, the acyl fluoride can be temporarily separated and then reacted again with the alcohol in the presence of a hydrogen fluoride catalyst. However, it is preferred to directly react with the alcohol to obtain the ester without separating the acyl fluoride. In this case, from the perspective of the corrosiveness of the reaction apparatus, a method in which a predetermined amount of alcohol is added to the acyl fluoride reaction solution is preferred.

[0144] The amount of the alcohol represented by formula (3) used is preferably 0.5 to 2.0 molar times, more preferably 0.8 to 1.5 molar times, relative to the compound represented by formula (2) as a raw material in the carbonylation step. A molar ratio of the alcohol of 0.5 molar times or more reduces the amount of unreacted fluoride remaining and minimizes corrosion of equipment in subsequent steps. Therefore, from the perspective of suppressing dehydration reactions between alcohol molecules and thus suppressing corrosion of equipment, the alcohol ratio is preferably 2.0 molar times or less.

[0145] From the viewpoint of suppressing ester decomposition, the reaction temperature of the acid fluoride and the alcohol is preferably 20° C. or lower. 20° C. or lower is preferred because the dehydration reaction between alcohol molecules can be suppressed.

[0146] After hydrogen fluoride is distilled off from the resulting ester, purification is performed using conventional methods such as distillation to obtain 1-ethylcyclohexanecarboxylate represented by formula (1). The resulting 1-ethylcyclohexanecarboxylate has an excellent herbal aroma and is therefore suitable for use as a fragrance. By incorporating it as an active ingredient in a fragrance composition, a fragrance composition having an herbal feel and excellent fragrance diffusivity can be obtained. In addition, according to this production method, 1-ethylcyclohexanecarboxylate can be efficiently obtained, making it industrially practical and capable of producing a fragrance having an excellent fragrance.

[0147] Example

[0148] The present invention will be specifically described based on the following examples, but the present invention is not limited to these examples.

[0149] [Analysis / Evaluation]

[0150] Purity (GC analysis)

[0151] The purity of 1-ethylcyclohexanecarboxylate obtained in Examples 1 to 4 was analyzed by gas chromatography (GC analysis). The conditions for GC analysis are shown below.

[0152] 〔GC analysis conditions〕

[0153] 100 mg of the sample (product from the example) was diluted with 2 mL of diethyl ether (manufactured by Fujifilm Wako Pure Chemical Corporation). The measurement apparatus used was an Agilent Technologies GC-6850, and the column used was a J&W DB-1 column (0.25 mm inner diameter, 30 m length, 0.25 μm film thickness). The temperature was increased at 10°C / min from 80°C to 300°C.

[0154] <Identification of compounds (GC-MS analysis, NMR spectrum analysis)>

[0155] Gas chromatography-mass spectrometry (GC-MS analysis) and NMR spectrum analysis were used to identify the 1-ethylcyclohexanecarboxylate obtained in Examples 1 to 4. The conditions for each analysis are shown below.

[0156] 〔GC-MS analysis conditions〕

[0157] A 10 mg sample (1-ethylcyclohexanecarboxylate) was diluted with 2 mL of diethyl ether (manufactured by Fujifilm Wako Pure Chemical Corporation). The measurement apparatus used was an Agilent Technologies 5977B GC / MSD, and the column used was a J&W HP-5 (0.25 mm inner diameter, 30 m length, 0.25 μm film thickness). The temperature was increased at 10°C / min from 80°C to 300°C. The MSD ionization method was EI.

[0158] [NMR spectrum analysis conditions]

[0159] 10 mg of a sample (1-ethylcyclohexanecarboxylate) was diluted with 0.8 mL of chloroform-d (99.8% deuteration rate, containing 0.05 vol% TMS, manufactured by FUJIFILM Wako Pure Chemical Corporation) and measured using Agilent-NMR-vnmrs400 manufactured by Varian. 1 H-NMR and 13 C-NMR.

[0160] <Fragrance Evaluation>

[0161] The 1-ethylcyclohexanecarboxylate obtained in the Examples and the fragrance compositions obtained in the Examples and Comparative Examples were subjected to sensory evaluation using odor test strips by four professional panelists with at least five years of evaluation experience.

[0162] [Synthesis of raw materials]

[0163] Preparation Example 1 (Synthesis of 4-ethylcyclohexene)

[0164] Into a 5 L stainless steel autoclave equipped with a magnetic induction stirrer, three inlet nozzles at the top, an extraction nozzle with a filter at the bottom, and internal temperature control via a jacket, 2.0 g of a Cu-Cr catalyst (trade name "N-203S" manufactured by JGC Catalysts & Chemicals Co., Ltd.) and 100 g of heptane (special grade manufactured by FUJIFILM Wako Pure Chemical Corporation) were placed, and activation was carried out at 170°C and a hydrogen pressure of 2 MPa for 1 hour.

[0165] After cooling, only the heptane was extracted from a filter-equipped extraction nozzle at the bottom. 50 g of 4-vinylcyclohexene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.25 g of heptane (special grade, manufactured by Fujifilm Wako Pure Chemical Corporation) were added, and a hydrogenation reaction was carried out by stirring at 50°C and a hydrogen pressure of 1 MPa for 5 hours. The reaction solution was filtered to remove the catalyst, and the resulting reaction solution was purified using a distillation column with 20 theoretical plates to obtain 45 g of 4-ethylcyclohexene.

[0166] [Production of 1-ethylcyclohexanecarboxylate]

[0167] Example 1 (Production of ethyl 1-ethylcyclohexanecarboxylate)

[0168] <Carbonylation process>

[0169] The experiment was conducted using a 500 mL stainless steel autoclave equipped with a magnetic induction stirrer, three inlet nozzles at the top, one extraction nozzle at the bottom, and capable of controlling the internal temperature with a jacket.

[0170] First, the interior of the autoclave was replaced with nitrogen, and then 120 g (6 mol) of hydrogen fluoride was introduced. After the liquid temperature was set to -10°C, the autoclave was pressurized to 2 MPa with carbon monoxide.

[0171] While maintaining the reaction temperature at -10°C and the reaction pressure at 2 MPa, a mixed solution of 67 g (0.6 mol) of 4-ethylcyclohexene and 67 g of heptane obtained in Production Example 1 was fed from the top of the autoclave over 45 minutes to carry out a carbonylation reaction. After completion of the feeding, stirring was continued for approximately 20 minutes until no more carbon monoxide absorption was observed.

[0172] <Esterification process>

[0173] Next, while the reaction temperature was maintained at -10°C, 41.7 g (0.9 mol) of ethanol was supplied from the top of the autoclave over 15 minutes, and esterification was performed for 1 hour under stirring.

[0174] The reaction mixture was drawn from the bottom of the autoclave into ice water, and after separation of the oil phase and aqueous phase, the oil phase was washed once with 100 mL of a 2% aqueous caustic soda solution and twice with 100 mL of distilled water, followed by dehydration with 10 g of anhydrous sodium sulfate. The resulting oil phase was purified using a distillation column with 20 theoretical plates to yield 78 g of ethyl 1-ethylcyclohexanecarboxylate as a colorless, transparent liquid. The results of the aroma evaluation of the resulting ethyl 1-ethylcyclohexanecarboxylate are shown in Table 1.

[0175] 〔Ethyl 1-ethylcyclohexanecarboxylate〕

[0176] The results of GC analysis showed that the purity of the main product was 99.7%. GC-MS analysis was performed on the main product and the results were 184 (10, M + ), 156(25), 129(24), 111(100), 69(74), 55(25), and confirmed that the molecular weight of the target compound was 184. 1 The analytical values ​​of H-NMR (CDCl3, 400 MHz, δ ppm) 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 further, 13 The analytical values ​​of C-NMR (CDCl3, 400 MHz, δppm) were 8.5 (CH3), 14.3 (CH3), 23.3 (CH2), 26.0 (CH2), 33.3 (CH2), 33.8 (CH2), 47.2 (C), 59.9 (OCH2), 176.8 (CO), and the main product was identified as ethyl 1-ethylcyclohexanecarboxylate.

[0177] Example 2 (Production of methyl 1-ethylcyclohexanecarboxylate)

[0178] The same procedure as in Example 1 was followed, except that 41.7 g (0.9 mol) of ethanol used in the esterification step was replaced with 27 g (0.84 mol) of methanol, to obtain 72 g of methyl 1-ethylcyclohexanecarboxylate as a colorless, transparent liquid. The results of the aroma evaluation of the obtained methyl 1-ethylcyclohexanecarboxylate are shown in Table 1.

[0179] 〔Methyl 1-ethylcyclohexanecarboxylate〕

[0180] The results of GC analysis showed that the purity of the main product was 99.8%. GC-MS analysis was performed on the main product and the results were 170 (13, M + ), 142(25), 115(44), 102(20), 69(100), 55(37), which were confirmed to be consistent with the molecular weight of the target substance, 170. 1 The analytical values ​​of H-NMR (CDCl3, 400 MHz, δ ppm) 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 further, 13The analytical values ​​of C-NMR (CDCl3, 400 MHz, δppm) were 8.6 (CH3), 23.3 (CH2), 26.0 (CH2), 33.3 (CH2), 33.8 (CH2), 47.5 (C), 51.4 (OCH3), 177.3 (CO), and the main product was identified as methyl 1-ethylcyclohexanecarboxylate.

[0181] Example 3 (Production of 1-ethylcyclohexanecarboxylic acid propyl ester)

[0182] The same procedure as in Example 1 was followed, except that 49 g (0.82 mol) of 1-propanol was used instead of 41.7 g (0.9 mol) of ethanol in the esterification step of Example 1, to obtain 78 g of 1-ethylcyclohexanecarboxylic acid propyl ester as a colorless, transparent liquid. The results of the aroma evaluation of the obtained 1-ethylcyclohexanecarboxylic acid propyl ester are shown in Table 1.

[0183] 〔1-Ethylcyclohexanecarboxylic acid propyl ester〕

[0184] The results of GC analysis showed that the purity of the main product was 98.7%. GC-MS analysis was performed on the main product and the results were 198 (5, M + ), 170(15), 157(18), 143(12), 111(100), 101(20), 69(68), 55(23), and confirmed that the molecular weight of the target compound was 198. 1 The analytical values ​​of H-NMR (CDCl3, 400 MHz, δ ppm) were 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), and further, 13 The analytical values ​​of C-NMR (CDCl3, 400 MHz, δppm) were 8.5 (CH3), 10.6 (CH3), 22.1 (CH2), 23.3 (CH2), 26.1 (CH2), 33.3 (CH2), 33.8 (CH2), 47.4 (C), 65.6 (OCH2), 176.9 (CO), and the main product was identified as 1-ethylcyclohexane propyl carboxylate.

[0185] Example 4 (Production of Isopropyl 1-Ethylcyclohexanecarboxylate)

[0186] The same procedure as in Example 1 was followed, except that 41.7 g (0.9 mol) of ethanol used in the esterification step was replaced with 46 g (0.76 mol) of 2-propanol, to obtain 71 g of isopropyl 1-ethylcyclohexanecarboxylate as a colorless, transparent liquid. The results of the aroma evaluation of the obtained isopropyl 1-ethylcyclohexanecarboxylate are shown in Table 1.

[0187] 〔Isopropyl 1-ethylcyclohexanecarboxylate〕

[0188] The results of GC analysis showed that the purity of the main product was 99.9%. GC-MS analysis was performed on the main product and the results were 198 (5, M + ), 170(15), 111(100), 1013(30), 69(78), 55(24), and confirmed that the molecular weight of the target compound was 198. 1 The analytical values ​​of H-NMR (CDCl3, 400 MHz, δ ppm) were 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), and further, 13 The analytical values ​​of C-NMR (CDCl3, 400 MHz, δppm) were 8.4 (CH3), 21.9 (CH3), 23.3 (CH2), 23.3 (CH2), 26.1 (CH2), 33.4 (CH2), 33.8 (CH2), 47.0 (C), 66.9 (OCH2), 176.2 (CO), and the main product was identified as isopropyl 1-ethylcyclohexanecarboxylate.

[0189] [Table 1]

[0190]

[0191] It was found that the 1-ethylcyclohexanecarboxylate obtained in Examples 1 to 4 has a herbal aroma and furthermore has fragrance diffusivity, and therefore is suitable for use as a fragrance. Furthermore, it was found that the 1-ethylcyclohexanecarboxylate obtained in Examples 1 to 4 is suitable for use in a fragrance imparting a herbal aroma. In particular, it was found that the ethyl 1-ethylcyclohexanecarboxylate obtained in Example 1 has a fruity aroma in addition to a herbal aroma, and therefore is suitable for use as a fragrance.

[0192] Examples 5 to 8 and Comparative Example 1 (Fragrance Compositions)

[0193] Floral fragrance compositions containing 1-ethylcyclohexanecarboxylate obtained in Examples 1 to 4 as a component were prepared. As a comparative example, a fragrance composition was prepared in which 1-ethylcyclohexanecarboxylate was replaced with dipropylene glycol as the solvent. The composition of the floral fragrance composition is shown in Table 2. The results of the fragrance evaluation of the floral fragrance composition are shown in Table 3.

[0194] [Table 2]

[0195] Table 2

[0196]

[0197] 1) Triplal: IFF (trade name), compound name: 2,4-dimethyl-3-cyclohexene-1-carbaldehyde

[0198] 2) MAGNOL: Kao Corporation (trade name), a mixture with ethyl norbornyl cyclohexanol as the main ingredient

[0199] 3) Undecavertol: Givaudan (trade name), compound name: 4-methyl-3-decen-5-ol

[0200] 4) POIRENATE: Kao Corporation (registered trademark), compound name: ethyl 2-cyclohexylpropionate

[0201] 5) Fruitate: Kao Corporation (registered trademark), compound name: Tricyclic [5.2.1.0 2,6 ]Ethyl decane-2-carboxylate

[0202] 6) Lilial: Givaudan (trade name), compound name: p-tert-butyl-α-methylhydrocinnamaldehyde

[0203] 7) AMBER CORE: Kao Corporation (registered trademark), compound name: 1-(2-tert-butylcyclohexyloxy)-2-butanol

[0204] 8) 50% IPM: 50% isopropyl myristate (IPM) solution

[0205] 9) AMBROXAN: Kao Corporation (registered trademark), compound name: Dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan

[0206] 10) 5% DPG: 5% dipropylene glycol (DPG) solution

[0207] [Table 3]

[0208] Table 3

[0209]

[0210] Example 9 and Comparative Example 2 (Fragrance Composition)

[0211] A sweet pea fragrance composition containing ethyl 1-ethylcyclohexanecarboxylate obtained in Example 1 as a component was prepared. As a comparative example, a fragrance composition was prepared in which 1-ethylcyclohexanecarboxylate was replaced with dipropylene glycol as the solvent. The composition of the sweet pea fragrance composition is shown in Table 4. The results of the fragrance evaluation of the sweet pea fragrance composition are shown in Table 5.

[0212] [Table 4]

[0213] Table 4

[0214]

[0215] [Table 5]

[0216] Table 5

[0217]

[0218] Example 10 and Comparative Example 3 (Fragrance Composition)

[0219] A peach-shaped fragrance composition containing ethyl 1-ethylcyclohexanecarboxylate obtained in Example 1 as a component was prepared. As a comparative example, a fragrance composition was prepared in which 1-ethylcyclohexanecarboxylate was replaced with dipropylene glycol as the solvent. The composition of the peach-shaped fragrance composition is shown in Table 6. The results of the aroma evaluation of the peach-shaped fragrance composition are shown in Table 7.

[0220] [Table 6]

[0221] Table 6

[0222]

[0223] [Table 7]

[0224] Table 7

[0225]

[0226] Compared to the fragrance compositions of the comparative examples, the fragrance compositions of the examples exhibited a herbal aroma and improved fragrance diffusivity. As shown in Tables 3, 5, and 7, the fragrance compositions of the examples possessed excellent fragrance properties with high diffusivity, making them particularly useful as fragrance-imparting ingredients in a wide range of toiletries, including laundry detergents and body cleansers. In particular, as shown in Examples 5 and 10, fragrance compositions containing ethyl 1-ethylcyclohexanecarboxylate as an active ingredient also exhibited a fruity aroma with excellent diffusivity, making them particularly useful as fragrance-imparting ingredients.

[0227] The above results demonstrate that the fragrance compositions of the Examples have a herbal aroma and excellent fragrance diffusivity. Furthermore, it is shown that the specific 1-ethylcyclohexanecarboxylate used in the Examples has a herbal aroma and can impart fragrance diffusivity, thus making it useful as a fragrance. Furthermore, it is shown that the specific 1-ethylcyclohexanecarboxylate used in the Examples can be suitably used in a method for imparting a herbal aroma.

Claims

1. A flavoring composition comprising 1-ethylcyclohexanecarboxylate represented by the following general formula (1) as an active ingredient, In formula (1), R 1 It 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 1-ethylcyclohexanecarboxylate represented by formula (1).

3. The flavor composition according to claim 2, wherein The fragrance substance other than 1-ethylcyclohexanecarboxylate 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 1-ethylcyclohexanecarboxylate represented by formula (1).

4. The flavor composition according to any one of claims 1 to 3, wherein R 1 It 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. The flavor composition according to any one of claims 1 to 4, wherein R 1 For ethyl.

6. Use of 1-ethylcyclohexanecarboxylate represented by the following general formula (1) as a fragrance, In formula (1), R 1 It represents an alkyl group having 1 to 3 carbon atoms.

7. The use according to claim 6, wherein: R 1 It 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 or 7, wherein: The 1-ethylcyclohexanecarboxylate represented by the formula (1) imparts a herbaceous aroma.

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

10. The use according to claim 9, wherein: The 1-ethylcyclohexanecarboxylate represented by the formula (1) imparts herbal and fruity aromas.

11. A method for imparting aroma, comprising imparting herbal aroma using 1-ethylcyclohexanecarboxylate 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.

12. The method for imparting fragrance according to claim 11, wherein: R 2 The 1-ethylcyclohexanecarboxylate represented by the formula (1a) is an ethyl group, and imparts herbal and fruity aromas.

13. A method for producing 1-ethylcyclohexanecarboxylate, wherein: In the presence of hydrogen fluoride, carbon monoxide and an alcohol represented by the following general formula (3) are reacted with a compound represented by the following general formula (2) to obtain 1-ethylcyclohexanecarboxylate represented by the following general formula (1). In formula (2), one of the carbon-carbon bonds including the dotted 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, wherein R 1 R in formula (3) 1 The same, represents an alkyl group having 1 to 3 carbon atoms.

14. The method for producing 1-ethylcyclohexanecarboxylate according to claim 13, wherein R 1 It 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. The method for producing 1-ethylcyclohexanecarboxylate according to claim 13 or 14, wherein R 1 For ethyl.

16. The method for producing 1-ethylcyclohexanecarboxylate according to any one of claims 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 1-ethylcyclohexanecarboxylate according to any one of claims 13 to 16, comprising the step of hydrogenating 4-vinylcyclohexene to obtain 4-ethylcyclohexene, wherein the compound represented by the general formula (2) is 4-ethylcyclohexene.

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