Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
  • C07C69/75—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a six-membered ring
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
  • A61K8/37—Esters of carboxylic acids
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q13/00—Formulations or additives for perfume preparations
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
  • C11B9/00—Essential oils; Perfumes
  • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
  • C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• Ester compounds are widely used as fragrances. Formates and acetates, in particular, are widely found in nature and often have a fruity scent. Synthetic fragrances that are ester compounds are also known.
• Non-Patent Document 1 describes that methyl 1-methyl-3-cyclohexenecarboxylate has a complex odor pronounced of chrysanthemum or thujone and is used as a fragrance.
• an object of the present invention is to provide a fragrance composition having a novel fragrance and properties, and use of a compound capable of imparting novel fragrance and properties to a fragrance composition, a fragrance imparting method, and a method for producing the compound.
• 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 that there is an efficient method for producing the ester compound, which led to the completion of the present invention.
• fragrance composition according to [2] above, wherein the fragrance substance other than the 1-ethylcyclohexane carboxylate 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-ethylcyclohexane carboxylate represented by formula (1).
• R 1 represents an alkyl group having 1 to 3 carbon atoms.
• 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.
• R 1 is an alkyl group having 1 to 3 carbon atoms.
• 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.
• R 8 The use according to the above [6] or [7], wherein the 1-ethylcyclohexane carboxylate represented by formula (1) imparts a herbal fragrance.
• R 1 is an ethyl group.
• a method for producing a 1-ethylcyclohexane carboxylate 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-ethylcyclohexane carboxylate represented by the following general formula (1):
• a compound represented by the following general formula (2) one of the carbon-carbon bonds including the dashed line is a double bond and the rest are single bonds.
• R 1 represents an alkyl group having 1 to 3 carbon atoms.
• R 1 is the same as R 1 in formula (3) and represents an alkyl group having 1 to 3 carbon atoms.
• 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.
• R 1 is an ethyl group.
• the present invention can provide a fragrance composition that has a herbal feel and excellent fragrance diffusibility by containing 1-ethylcyclohexane carboxylate as an active ingredient, which can impart a herbal fragrance and further impart fragrance diffusibility, the use of 1-ethylcyclohexane carboxylate as a fragrance, and a method for producing 1-ethylcyclohexane carboxylate.
• XX-YY means "XX or more and YY or less.”
• the fragrance composition of the present invention is a fragrance composition containing, as an active ingredient, a 1-ethylcyclohexane carboxylate represented by the following general formula (1).
• R 1 represents an alkyl group having 1 to 3 carbon atoms.
• the fragrance composition of the present invention can impart a herbal fragrance and further contains 1-ethylcyclohexane carboxylate as an active ingredient, which can impart fragrance diffusibility, and therefore has a herbal feel and excellent fragrance diffusibility. Therefore, it is useful as a fragrance component for various products.
• R 1 represents an alkyl group having 1 to 3 carbon atoms. Specifically, R 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.
• R 1 is an ethyl group
• the compound has a fruity scent in addition to an herbal scent, and is therefore very useful as an active ingredient in a fragrance composition.
• the 1-ethylcyclohexane carboxylate 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 further impart fragrance diffusibility.
• R 1 is a methyl group, it has a particularly easily diffusible herbal fragrance.
• R 1 is an ethyl group, it has a particularly well-diffusible herbal fragrance and fruity fragrance.
• R 1 is an n-propyl group, it has a particularly easily diffusible herbal fragrance.
• R 1 is an isopropyl group, it has a particularly easily diffusible herbal fragrance.
• the content of the 1-ethylcyclohexane carboxylate in the fragrance composition of the present invention may be adjusted as appropriate depending on the type of fragrance composition, the type of desired fragrance, the strength of the fragrance, etc., and is preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass, even more preferably 0.02 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.
• fragrance substances other than the 1-ethylcyclohexane carboxylate represented by formula (1), surfactants, solvents, antioxidants, colorants, etc. and at least one selected from the group consisting of fragrance substances other than the 1-ethylcyclohexane carboxylate 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 carboxylate represented by formula (1) and solvents is more preferred, and a fragrance substance other than the 1-ethylcyclohexane carboxylate represented by formula (1) is even more preferred.
• a preferred fragrance composition of the present invention contains the 1-ethylcyclohexane carboxylate represented by formula (1) as an active ingredient, and contains a fragrance substance other than the 1-ethylcyclohexane carboxylate represented by formula (1).
• a fragrance substance other than the 1-ethylcyclohexane carboxylate represented by formula (1) the scent can be adjusted to suit the target product.
• a solvent it becomes easy to dissolve and impregnate the target product, and the strength and persistence of the scent can be adjusted.
• a floral-type fragrance composition using a fragrance substance other than the 1-ethylcyclohexane carboxylate represented by formula (1), and it is preferable to contain the 1-ethylcyclohexane carboxylate represented by formula (1) as an active ingredient in a floral-type fragrance composition.
• fragrance substances other than the 1-ethylcyclohexane carboxylate 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 can be selected and used alone or in any mixture of two or more kinds in any ratio:
• the fragrance substance other than the 1-ethylcyclohexane carboxylate 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-ethylcyclohexane carboxylate represented by formula (1), more preferably at least one selected from the group consisting of alcohols, aldehydes, and esters other than the 1-ethylcyclohexane carboxylate represented by formula (1), and even more preferably at least one selected from the group consisting of alcohols and aldehydes.
• hydrocarbons examples include limonene, ⁇ -pinene, ⁇ -pinene, terpinene, cedrene, longifolene, and valencene.
• alcohols include linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenol, ethyl linalool, farnesol, nerolidol, cis-3-hexenol, cedrol, menthol, borneol, ⁇ -phenylethyl alcohol, benzyl alcohol, phenylhexanol, 2,2,6-trimethylcyclohexyl-3-hexanol, 1-(2-t-butylcyclohexyloxy)-2-butanol, 4-isopropylcyclohexyl, 1-(2-tert-butylcyclohexyloxy)-2-butanol ...
• 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.
• phenols include eugenol, thymol, and vanillin.
• 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, tricyclodecenyl propionate, onate, allyl cycl
• aldehydes examples include n-octanal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecenal, citronellal, citral, hydroxycitronellal, dimethyltetrahydrobenzaldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, 2-cyclohexylpropanal, p-t-butyl- ⁇ -methylhydrocinnamic aldehyde, p-t-butylhydrocinnamic aldehyde, p-isopropyl- ⁇ -methylhydrocinnamic aldehyde, p-ethyl- ⁇ , ⁇ -dimethylhydrocinnamic aldehyde, ⁇ -amylcinnamic aldehyde, ⁇ -hexylcinnamic aldehyde, piper
• ketones include methylheptenone, 4-methylene-3,5,6,6-tetramethyl-2-heptanone, amylcyclopentanone, 3-methyl-2-(cis-2-penten-1-yl)-2-cyclopenten-1-one, methylcyclopentenolone, rose ketone, ⁇ -methylionone, ⁇ -ionone, carvone, menthone, camphor, nootkatone, benzylacetone, anisylacetone, methyl ⁇ -naphthyl ketone, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, maltol, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, muscone, civetone, cyclopentadecanone, and cyclohexadecenone.
• acetals and ketals examples include acetaldehyde ethyl phenyl propyl acetal, citral diethyl acetal, phenylacetaldehyde glycerin acetal, and ethyl acetoacetate ethylene glycol ketal.
• the ethers include anethole, ⁇ -naphthyl methyl ether, ⁇ -naphthyl ethyl ether, limonene oxide, rose oxide, 1,8-cineole, racemic or optically active dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan, and the like.
• the nitriles include citronellyl nitrile.
• lactones include ⁇ -nonalactone, ⁇ -undecalactone, ⁇ -decalactone, ⁇ -jasmolactone, coumarin, cyclopentadecanolide, cyclohexadecanolide, ambrettelide, ethylene brassylate, and 11-oxahexadecanolide.
• natural essential oils and extracts include orange, lemon, bergamot, mandarin, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, geranium, jasmine, ylang-ylang, anise, clove, ginger, nutmeg, cardamom, cedar, cypress, sandalwood, vetiver, patchouli, and labdanum.
• the solvent examples include dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, and triethyl citrate.
• the surfactant may, for example, be polyoxyethylene lauryl sulfate ether.
• the fragrance composition containing the 1-ethylcyclohexane carboxylate represented by the general formula (1) can be used as a fragrance component for various products.
• examples of products in which the fragrance composition can be used include fragrance products such as perfumes and colognes; shampoos, rinses, hair tonics, hair creams, mousses, gels, pomades, sprays, and other hair cosmetics; skin cosmetics such as lotions, beauty essences, creams, milky lotions, packs, foundations, face powders, lipsticks, and various types of make-up; dishwashing detergents, laundry detergents, softeners, disinfectant detergents, deodorizing detergents, room air fresheners, furniture care, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, germicides, repellents, and other various health and hygiene detergents; quasi-drugs such as toothpaste, mouthwash, bath additives, antiperspirant products, and perm solutions; miscellaneous goods such as toilet paper and tissue paper; medicines, etc
• 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.
• 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. Also, it is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less.
• the amount of the fragrance composition in the product may be 80% by mass or more, or may be 100% by mass.
• 1-Ethylcyclohexane carboxylate represented by the following general formula (1) has an excellent herbal scent and can be used as a fragrance.
• the use of 1-ethylcyclohexane carboxylate represented by the following general formula (1) as a fragrance is also included in the present invention.
• R 1 represents an alkyl group having 1 to 3 carbon atoms.
• R 1 represents an alkyl group having 1 to 3 carbon atoms. Specifically, R 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.
• R 1 is an ethyl group
• the compound has a fruity scent in addition to an herbal scent, and can therefore be more suitably used as a fragrance.
• the 1-ethylcyclohexane carboxylate represented by the above formula (1) has an excellent herbal fragrance. Therefore, the use of the 1-ethylcyclohexane carboxylate represented by the formula (1) imparts a herbal fragrance.
• R 1 is an ethyl group, it has a fruity fragrance in addition to a herbal fragrance, so when R 1 is an ethyl group, the use of the 1-ethylcyclohexane carboxylate represented by the formula (1) imparts both a herbal fragrance and a fruity fragrance.
• R 1 is a methyl group, it has a particularly easily diffusible herbal fragrance.
• R 1 is an ethyl group, it has a particularly well-diffusible herbal fragrance and fruity fragrance.
• R 1 is an n-propyl group, it has a particularly easily diffusible herbal fragrance.
• R 1 is an isopropyl group, it has a particularly easily diffusible herbal fragrance.
• the 1-ethylcyclohexane carboxylate represented by formula (1) can be used as a fragrance component of various products.
• the 1-ethylcyclohexane carboxylate represented by formula (1) is used as a fragrance component of various products, it may be used as one component of the fragrance composition.
• Examples of products in which the 1-ethylcyclohexane carboxylate represented by formula (1) can be used include fragrance products such as perfumes and colognes; shampoos, rinses, hair tonics, hair creams, mousses, gels, pomades, sprays, and other hair cosmetics; skin cosmetics such as lotions, beauty essences, creams, milky lotions, packs, foundations, face powders, lipsticks, and various types of make-up; dishwashing detergents, laundry detergents, softeners, disinfectant detergents, deodorizing detergents, room fresheners, furniture care products, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, germicides, repellents, and other various health and hygiene detergents; quasi-drugs such as toothpaste, mouthwash, bath additives, antiperspirant products, and perm solution; miscellaneous goods such as toilet paper and tissue paper; medicines, and the like; and foods, and the like.
• fragrance products such as perfumes and colognes
• the amount of the 1-ethylcyclohexane carboxylate 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.
• the amount of the 1-ethylcyclohexane carboxylate 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. Also, it is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less.
• the blending amount of the 1-ethylcyclohexane carboxylate represented by the formula (1) in the product may be 80 mass% or more, or may be 100 mass%.
• 1-Ethylcyclohexane carboxylate represented by the following general formula (1a) has an excellent herbal fragrance and can impart a herbal fragrance to various products.
• the present invention also includes a fragrance imparting method for imparting a herbal fragrance using 1-ethylcyclohexane carboxylate represented by the following general formula (1a).
• the method of imparting a herbal scent to a product may be, for example, coating, spraying, or immersion when the product is solid, or mixing when the product is liquid.
• the 1-ethylcyclohexane carboxylate represented by formula (1a) may be used as one component of the fragrance composition to impart a herbal scent to various products.
• R2 represents at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
• 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, 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.
• R 1 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.
• the 1-ethylcyclohexane carboxylate represented by the above formula (1a) has an excellent herbal fragrance and can impart a herbal fragrance to various products.
• R 1 is an ethyl group, it has a fruity fragrance in addition to the herbal fragrance, so when R 1 is an ethyl group, the 1-ethylcyclohexane carboxylate represented by the formula (1a) can impart both a herbal fragrance and a fruity fragrance to various products.
• R 1 is a methyl group, it has a particularly easily diffusible herbal fragrance and imparts a herbal fragrance to the product.
• R 1 When R 1 is an ethyl group, it has a particularly well-diffusible herbal fragrance and fruity fragrance, imparting a herbal fragrance and fruity fragrance to the product. When R 1 is an n-propyl group, it has a particularly easily diffusible herbal fragrance and imparts a herbal fragrance to the product. When R 1 is an isopropyl group, it has a particularly easily diffusible herbal fragrance and imparts a herbal fragrance to the product.
• Products that can be imparted with a herbal fragrance by the 1-ethylcyclohexane carboxylate represented by formula (1a) include, for example, fragrance products such as perfumes and colognes; shampoos, rinses, hair tonics, hair creams, mousses, gels, pomades, sprays, and other hair cosmetics; skin cosmetics such as lotions, beauty essences, creams, milky lotions, packs, foundations, face powders, lipsticks, and various types of make-up; dishwashing detergents, laundry detergents, softeners, disinfectant detergents, deodorizing detergents, room fresheners, furniture care, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, germicides, repellents, and other various health and hygiene detergents; quasi-drugs such as toothpaste, mouthwash, bath additives, antiperspirant products, and perm solution; miscellaneous goods such as toilet paper and tissue paper; medicines, and foods, etc.
• fragrance products such as perfumes and
• the amount of the 1-ethylcyclohexane carboxylate 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.
• the amount of the 1-ethylcyclohexane carboxylate 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, more preferably 60% by mass or less, and even more preferably 40% by mass or less.
• the blending amount of the 1-ethylcyclohexane carboxylate represented by the formula (1a) in the product may be 80 mass% or more, or may be 100 mass%.
• the method for producing a 1-ethylcyclohexanecarboxylate of the present invention is a method for producing a 1-ethylcyclohexanecarboxylate, 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-ethylcyclohexanecarboxylate 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 rest are single bonds.
• R 1 represents an alkyl group having 1 to 3 carbon atoms.
• R 1 is the same as R 1 in formula (3) and represents an alkyl group having 1 to 3 carbon atoms.)
• the compound represented by formula (2) is any one of a compound represented by the following formula (2a), a compound represented by the following formula (2b), and a compound represented by the following formula (2c). Preferably, it is at least one selected from the group consisting of a compound represented by the following formula (2a) and a compound represented by the following formula (2b), and more preferably, it is a compound represented by formula (2a).
• the compound represented by formula (2a) is 4-ethylcyclohexene
• 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.
• 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, preferably, the method includes a step of hydrogenating 4-vinylcyclohexene to obtain 4-ethylcyclohexene.
• the reaction formula is shown below.
• reaction conditions for the hydrogenation there are no particular limitations on the reaction conditions for the hydrogenation, but the reaction may be carried out under reaction conditions typically used for hydrogenating unsaturated bonds.
• a catalyst for the 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 preferable. Specific examples include catalysts containing at least one of 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.
• solid catalysts examples include unsupported metal catalysts and supported metal catalysts.
• Preferred examples of 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, etc.
• 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 or mixed on a carrier such as magnesia, zirconia, ceria, diatomaceous earth, activated carbon, alumina, silica, zeolite, or titania.
• 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.
• 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
• supported rhodium catalysts such as Rh/C or Rh/alumina.
• the amount of hydrogenation catalyst used varies depending on the type of catalyst, but is typically 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.
• the hydrogen pressure can be either normal pressure or pressurized, but is usually 0.1 to 4.0 MPa, preferably 0.1 to 3.0 MPa, and more preferably 0.1 to 2.0 MPa.
• the hydrogenation reaction can be carried out without a solvent, but a solvent may also be used.
• solvents 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 of these.
• the amount of 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 raw material 4-vinylcyclohexene.
• the reaction temperature for the hydrogenation reaction is usually -90°C to 200°C, preferably 20°C to 150°C, and more preferably 20°C to 100°C.
• 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. Examples include a suspended bed reactor in which the catalyst is fluidized with a fluid to carry out catalytic hydrogenation, and a fixed bed reactor in which the catalyst is filled and fixed and a fluid is supplied to carry out catalytic hydrogenation.
• the alcohol represented by formula (3) is a monohydric alcohol having an alkyl group having 1 to 3 carbon atoms.
• R 1 in formula (3) is an alkyl group having 1 to 3 carbon atoms, and specifically, R 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.
• the alcohol represented by formula (3) is preferably methanol, ethanol, 1-propanol, or 2-propanol, and more preferably ethanol.
• the production method of the present invention involves reacting a compound represented by formula (2) with carbon monoxide and an alcohol represented by formula (3) in the presence of hydrogen fluoride to obtain a 1-ethylcyclohexanecarboxylate represented by formula (1).
• the compound is carbonylated using carbon monoxide, and the resulting carbonyl compound is reacted with an alcohol to obtain a 1-ethylcyclohexanecarboxylate represented by formula (1).
• the carbonylation reaction will be described, followed by the conversion to an ester.
• Hydrogen fluoride used in the carbonylation reaction is a solvent, a catalyst, and a secondary raw material, and is therefore 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). If 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-ethylcyclohexane carboxylate represented by formula (1), can be obtained in high yield. From the viewpoint of raw material costs and productivity, the molar ratio of hydrogen fluoride is preferably 15 or less.
• the carbon monoxide used in the carbonylation reaction may contain inert gases such as nitrogen and methane, but the carbon monoxide partial pressure during the reaction is preferably 0.5 to 5 MPa, and 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 at the same time, making it possible to obtain the target product, 1-ethylcyclohexane carboxylate represented by formula (1), in high yield. In addition, from the viewpoint of equipment load, it is preferable that the carbon monoxide partial pressure be 5 MPa or less.
• the carbonylation reaction method is not particularly limited, and may be any method such as a batch method, a semi-continuous method, or a continuous method.
• 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. If the reaction temperature of the carbonylation reaction is 30° C. or lower, the yield is good. From the viewpoint of the reaction rate, the reaction is preferably carried out at ⁇ 50° C. or higher.
• an acid fluoride is produced from hydrogen fluoride and carbon monoxide.
• the acid fluoride reaction solution produced may be purified by standard methods such as distillation after excess hydrogen fluoride has been removed, but it is preferable to react it directly with an alcohol to convert it into an ester.
• the acid fluoride when the reaction solution produced by the carbonylation reaction is reacted with an alcohol to synthesize an ester, the acid fluoride may be separated once and then reacted with an alcohol again under hydrogen fluoride catalyst, but it is preferable to react the acid fluoride directly with an alcohol without separating it to obtain an ester. From the viewpoint of the corrosiveness of the reaction apparatus, it is preferable to add a predetermined amount of alcohol to the acid fluoride reaction solution.
• the amount of the alcohol represented by formula (3) used is preferably 0.5 to 2.0 times by mole, and 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 process. If the molar ratio of the alcohol is 0.5 times or more, the amount of unreacted fluoride remaining is small and corrosion of the equipment in the subsequent process is small, which is preferable, and from the viewpoint of suppressing corrosion of the equipment by suppressing dehydration reactions between alcohol molecules, a molar ratio of 2.0 times or less is preferable.
• the reaction temperature between the acid fluoride and the alcohol is preferably 20°C or less in order to prevent the decomposition of the ester.
• a temperature of 20°C or less is preferable because it can prevent dehydration reactions between alcohol molecules.
• 1-ethylcyclohexane carboxylate represented by formula (1).
• the obtained 1-ethylcyclohexane carboxylate has an excellent herbal scent and can be suitably used as a fragrance, and by including it in a fragrance composition as an active ingredient, a fragrance composition can be obtained that has a herbal feel and excellent fragrance diffusion properties.
• 1-ethylcyclohexane carboxylate can be efficiently obtained, and therefore a fragrance that is industrially practical and has an excellent scent can be obtained.
• the measurement device 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 ⁇ m)."
• the temperature rise condition was 10° C./min from 80° C. to 300° C.
• the ionization method for the MSD was EI.
• Example 1 (Preparation of ethyl 1-ethylcyclohexanecarboxylate) ⁇ Carbonylation step> The 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 outlet nozzle at the bottom, and with a jacket that controlled the internal temperature. First, the inside of the autoclave was replaced with nitrogen, and then 120 g (6 moles) of hydrogen fluoride was introduced. The liquid temperature was adjusted to -10°C, and the pressure was increased to 2 MPa with carbon monoxide.
• the obtained oil phase was purified in a distillation column with 20 theoretical plates, and 78 g of ethyl 1-ethylcyclohexanecarboxylate was obtained as a colorless, transparent liquid.
• the results of the aroma evaluation of the obtained ethyl 1-ethylcyclohexanecarboxylate are shown in Table 1.
• Example 2 (Preparation of methyl 1-ethylcyclohexanecarboxylate) Except for changing the 41.7 g (0.9 mol) of ethanol used in the esterification step of Example 1 to 27 g (0.84 mol) of methanol, the same procedure as in Example 1 was repeated to obtain 72 g of methyl 1-ethylcyclohexanecarboxylate as a colorless, transparent liquid. The results of the odor evaluation of the obtained methyl 1-ethylcyclohexanecarboxylate are shown in Table 1.
• Example 3 (Preparation of propyl 1-ethylcyclohexanecarboxylate) Except for changing the 41.7 g (0.9 mol) of ethanol used in the esterification step of Example 1 to 49 g (0.82 mol) of 1-propanol, the same procedure as in Example 1 was repeated to obtain 78 g of 1-ethylcyclohexanepropyl carboxylate as a colorless, transparent liquid. The results of the odor evaluation of the obtained 1-ethylcyclohexanepropyl carboxylate are shown in Table 1.
• Example 4 Preparation of isopropyl 1-ethylcyclohexanecarboxylate Except for changing the 41.7 g (0.9 mol) of ethanol used in the esterification step of Example 1 to 46 g (0.76 mol) of 2-propanol, the same procedure as in Example 1 was repeated to obtain 71 g of isopropyl 1-ethylcyclohexanecarboxylate as a colorless, transparent liquid. The results of the odor evaluation of the obtained isopropyl 1-ethylcyclohexanecarboxylate are shown in Table 1.
• the 1-ethylcyclohexane carboxylate esters obtained in Examples 1 to 4 have a herbal scent and are diffusible, and therefore can be suitably used as fragrances. Furthermore, the 1-ethylcyclohexane carboxylate esters obtained in Examples 1 to 4 can be suitably used in fragrance methods that impart a herbal scent. In particular, the ethyl 1-ethylcyclohexane carboxylate obtained in Example 1 has a fruity scent in addition to a herbal scent, and therefore can be suitably used as a fragrance.
• Floral-type fragrance compositions were prepared containing the 1-ethylcyclohexane carboxylates obtained in Examples 1 to 4 as blending components.
• a fragrance composition was prepared in which the 1-ethylcyclohexane carboxylate 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.
• Example 9 and Comparative Example 2 A fragrance composition with a sweet pea scent was prepared, containing the ethyl 1-ethylcyclohexanecarboxylate obtained in Example 1 as a blending component.
• a fragrance composition was prepared in which 1-ethylcyclohexanecarboxylate 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.
• Example 10 and Comparative Example 3 A peach-type fragrance composition was prepared containing the ethyl 1-ethylcyclohexanecarboxylate obtained in Example 1 as a blending component.
• a fragrance composition was prepared in which the 1-ethylcyclohexanecarboxylate 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.
• fragrance compositions of the Examples had a herbal feel and improved fragrance diffusion compared to the fragrance compositions of the Comparative Examples.
• Tables 3, 5, and 7 the fragrance compositions of the Examples have excellent fragrance characteristics with excellent diffusion, and are therefore useful as fragrance ingredients for a wide range of toiletry products, particularly laundry detergents and body cleansers.
• fragrance compositions containing ethyl 1-ethylcyclohexanecarboxylate as an active ingredient are extremely useful as fragrance ingredients, as they also have a fruity feel with excellent diffusion, as shown in Examples 5 and 10.
• the fragrance compositions of the examples have a herbal feel and are excellent in fragrance diffusibility.
• the specific 1-ethylcyclohexane carboxylate ester used in the examples has a herbal fragrance and can further impart fragrance diffusibility, and therefore can be used as a fragrance.
• the specific 1-ethylcyclohexane carboxylate ester used in the examples can be suitably used in a fragrance-giving method that imparts a herbal fragrance.

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