Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
  • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
• • 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
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
  • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
  • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
  • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C31/13—Monohydroxylic alcohols containing saturated rings

Definitions

• the present invention relates to a fragrance composition, the use of an alicyclic alcohol as a fragrance, a method for producing an alicyclic alcohol, and an alicyclic alcohol composition.
• Non-Patent Document 1 The alicyclic alcohol 4-isopropylcyclohexanemethanol (Mayol) is a colorless liquid with a floral scent, and is used as a raw material for floral and woody compound fragrances (Non-Patent Document 1). It is also known that it can be produced by reducing perillaldehyde, and can be synthesized from ⁇ -pinene via perillic alcohol (Non-Patent Document 1).
• floral fragrances and blended fragrances are used in various fields such as fragrance products, cosmetics, detergents, sanitary products, miscellaneous goods, medicines, food, etc.
• new scents are being developed.
• 4-isopropylcyclohexanemethanol has a floral fragrance as mentioned above, but there is a demand for perfumes having even more novel fragrances. Therefore, an object of the present invention is to provide a fragrance and a fragrance composition having a novel scent.
• the inventors produced various alicyclic alcohols and alicyclic alcohol compositions and evaluated their aromas, discovering that certain alicyclic alcohols and alicyclic alcohol compositions have excellent aromas and are suitable for use as fragrances, and are also excellent as active ingredients in fragrance compositions, leading to the completion of the present invention.
• a fragrance composition comprising an alicyclic alcohol represented by the following formula (1) as an active ingredient: [2] The fragrance composition according to the above [1], further comprising at least one selected from the group consisting of fragrances other than the alicyclic alcohol represented by formula (1), surfactants, solvents, antioxidants and colorants.
• a fragrance other than the alicyclic alcohol represented by formula (1) or the alicyclic alcohol represented by formula (2) a surfactant, a solvent, an antioxidant, and a colorant.
• the present invention provides a fragrance composition that contains an alicyclic alcohol as an active ingredient, which can impart the smooth, clean, and natural scent of lily of the valley to the fragrance composition, has a clear, smooth, clean, and natural scent of lily of the valley, and has a clean, green, floral scent, as well as the use of the alicyclic alcohol as a fragrance, and an alicyclic alcohol composition that contains the alicyclic alcohol and its isomer.
• XX-YY means "XX or more and YY or less.”
• the fragrance composition of the present invention is a fragrance composition containing an alicyclic alcohol represented by the following formula (1) as an active ingredient.
• the compound represented by the following formula (1) is 3-isopropylcyclohexanemethanol.
• the fragrance composition of the present invention contains the alicyclic alcohol as an active ingredient, which can impart a smooth, clean, and natural lily of the valley scent to the fragrance composition.
• the fragrance composition of the present invention not only has the smooth, clean, and natural Lily of the valley scent that the alicyclic alcohol has, but also has a transparent, smooth, clean, and natural Lily of the valley scent and a clean, green floral scent, and is therefore useful as a fragrance component for various products.
• the content of the alicyclic alcohol represented by formula (1) 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., but is preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass, even more preferably 0.2 to 40% by mass, even more preferably 0.5 to 30% by mass, even more preferably 1 to 25% by mass, even more preferably 3 to 20% by mass, and even more preferably 4 to 15% by mass.
• fragrances other than the alicyclic alcohol represented by formula (1) contained in the fragrance composition containing the alicyclic alcohol represented by formula (1) include fragrances other than the alicyclic alcohol represented by formula (1), surfactants, solvents, antioxidants, colorants, etc., and are preferably at least one selected from the group consisting of fragrances other than the alicyclic alcohol represented by formula (1), surfactants, solvents, antioxidants, and colorants, and more preferably at least one selected from the group consisting of fragrances other than the alicyclic alcohol represented by formula (1) and solvents.
• the fragrance 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 fragrance can be adjusted.
• a fragrance composition having at least one of a floral-like and a fruity-like scent with a fragrance substance other than the alicyclic alcohol represented by formula (1) it is more preferable to compose a fragrance composition having a floral-like scent, and it is even more preferable to compose a fragrance composition having both a floral-like and a fruity-like scent.
• alicyclic alcohol represented by formula (1) it is preferable to contain the alicyclic alcohol represented by formula (1) as an active ingredient in a fragrance composition having at least one of a floral-like and a fruity-like scent, it is more preferable to contain it as an active ingredient in a fragrance composition having a floral-like scent, and it is even more preferable to contain it as an active ingredient in a fragrance composition having both a floral-like and a fruity-like scent.
• the fragrance other than the alicyclic alcohol represented by formula (1) is not particularly limited as long as it is a conventionally known fragrance component, and a wide range of fragrances can be used.
• the following can be selected and used alone or in any mixture ratio of two or more:
• Fragrances other than the alicyclic alcohol represented by formula (1) include hydrocarbons, alcohols, phenols, esters, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, natural essential oils, natural extracts, etc., and are preferably one or more fragrances selected from the group consisting of hydrocarbons, alcohols, phenols, esters, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, natural essential oils, and natural extracts.
• the fragrance other than the alicyclic alcohol represented by formula (1) is preferably at least one selected from the group consisting of aldehydes, natural essential oils, natural extracts, ethers, and esters, more preferably at least one selected from the group consisting of ethers and esters, and even more preferably esters.
• 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 ...
• Examples of the alcohols include cyclohexanemethanol, 4-t-butylcyclohexanol, 4-methyl-2-(2-methylpropyl)tetrahydro-2H-pyran-4-ol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, isocamphylcyclohexanol, and 3,7-dimethyl-7-methoxyoctan-2-ol.
• the alcohols are alcohols other than the alicyclic alcohols represented by formula (1).
• Examples of phenols include eugenol, thymol, and vanillin.
• Examples of esters include linalyl formate, citronellyl formate, geranyl formate, n-hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, terpinyl acetate, nopyr acetate, bornyl acetate, isobornyl acetate, o-t-butylcyclohexyl acetate, p-t-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styrallyl acetate, cinnamyl acetate, dimethylbenzylcarbinyl acetate, 3-pentyltetrahydropyran-4-yl acetate, citrone
• aldehydes examples include n-octanal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecenal, citronellal, citral, hydroxycitronellal, dimethyltetrahydrobenzaldehyde, 4(3)-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, 2-cyclohexylpropanal, p-t-butyl- ⁇ -methylhydrocinnamic aldehyde, p-isopropyl- ⁇ -methylhydrocinnamic aldehyde, p-ethyl- ⁇ , ⁇ -dimethylhydrocinnamic aldehyde, ⁇ -amylcinnamic aldehyde, ⁇ -hexylcinnamic aldehyde, piperonal, and ⁇ -methyl-3,4-methylenedioxyhydrocin
• 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 be polyoxyethylene alkyl sulfate ether, and polyoxyethylene lauryl sulfate ether is preferred.
• the fragrance composition containing the alicyclic alcohol represented by formula (1) has a transparent, smooth, clean and natural lily of the valley scent and a clean, green floral scent, and therefore can be used as a fragrance component for various products.
• products in which the fragrance composition can be used include fragrance products such as perfumes and colognes; hair cosmetics such as shampoos, conditioners, hair tonics, hair creams, mousses, gels, pomades, sprays, and other hair cosmetics; skin cosmetics such as lotions, beauty essences, creams, milky lotions, packs, foundations, face powders, lipsticks, and various types of make-up; dishwashing detergents, laundry detergents, softeners, disinfectant detergents, deodorizing detergents, indoor air fresheners, furniture care, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, germicides, repellents, and other various health and hygiene detergents; quasi-drugs such as toothpaste, mouthwash, bath additives, antiperspirant products, and
• the blending amount of the fragrance composition in the above-mentioned product is not particularly limited, and the blending amount of the fragrance composition can be selected according to the type, properties, and sensory effect of the product to be scented.
• the blending amount of the fragrance composition in the product is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.001% by mass or more. Also, it is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less.
• the amount of the fragrance composition in the product may be 80% by mass or more, or may be 100% by mass.
• the alicyclic alcohol represented by formula (1) has a smooth, clean, and natural lily of the valley scent and can impart a smooth, clean, and natural lily of the valley scent to a fragrance composition, and therefore can be used as a fragrance.
• the use of the alicyclic alcohol represented by the following formula (1) as a fragrance is also included in the present invention.
• the compound represented by formula (1) above is 3-isopropylcyclohexanemethanol.
• the alicyclic alcohol represented by the formula (1) may be produced by any method, but is preferably produced by the following method.
• a preferred method for producing the alicyclic alcohol represented by the formula (1) is a method in which an aromatic aldehyde represented by the following formula (3) is hydrogenated to obtain the alicyclic alcohol represented by the following formula (1).
• the aromatic aldehyde represented by formula (3) is 3-isopropylbenzaldehyde.
• the hydrogenation method is not particularly limited, and can be carried out by a known method using a hydrogenation catalyst.
• the hydrogenation catalyst is not particularly limited, and any known catalyst can be used.
• the hydrogenation catalyst is preferably a supported heterogeneous hydrogenation catalyst, a Ziegler type hydrogenation catalyst, a homogeneous hydrogenation catalyst, or a sponge metal catalyst.
• the supported heterogeneous hydrogenation catalyst is a catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like.
• the Ziegler type hydrogenation catalyst uses a transition metal salt and a reducing agent such as organoaluminum, etc.
• the transition metal salt include organic acid salts or acetylacetone salts of Ni, Co, Fe, Cr, etc.
• the homogeneous hydrogenation catalyst include organometallic compounds of Ti, Ru, Rh, Zr, etc.
• sponge metal catalysts include sponge nickel and sponge cobalt.
• the temperature of the hydrogenation reaction in this step is, from the viewpoints of suppressing reactivity and side reactions, preferably 0° C. or higher, more preferably 10° C. or higher, even more preferably 20° C. or higher, and preferably 150° C. or lower, even more preferably 120° C. or lower.
• the pressure of hydrogen used in the hydrogenation reaction is preferably 0.01 MPaG or more, more preferably 0.03 MPaG or more, even more preferably 0.05 MPaG or more, and preferably 10 MPaG or less, more preferably 3 MPaG or less, even more preferably 1 MPaG or less, and still more preferably 0.5 MPaG or less.
• the reaction time is not particularly limited, but is preferably 3 minutes or more, more preferably 10 minutes or more, even more preferably 30 minutes or more, and is preferably 24 hours or less, more preferably 12 hours or less, even more preferably 8 hours or less.
• the hydrogenation reaction may be carried out in the presence of a solvent.
• the solvent to be used is not particularly limited as long as it does not inhibit the hydrogenation reaction, but is preferably a hydrocarbon solvent, and more preferably at least one selected from the group consisting of aliphatic hydrocarbons and alicyclic hydrocarbons.
• the aliphatic hydrocarbon include pentane, hexane, isopentane, heptane, octane, and isooctane.
• the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. These may be used alone or in combination of two or more.
• the method for purifying the target alicyclic alcohol represented by formula (1) from the solution after the reaction is completed is not particularly limited, and any known method may be appropriately selected. Specific examples include filtration, chromatography, distillation purification, etc., and the target alicyclic alcohol with high purity can be obtained by purifying using an appropriate combination of these.
• the alicyclic alcohol composition of the present invention is an alicyclic alcohol composition containing an alicyclic alcohol represented by the following formula (1) and an alicyclic alcohol represented by the following formula (2).
• the alicyclic alcohol composition has a smooth and soft lily of the valley scent and can impart a smooth and soft lily of the valley scent to the fragrance composition.
• the alicyclic alcohol composition has a particularly soft lingering scent.
• the compound represented by formula (1) is 3-isopropylcyclohexanemethanol.
• the compound represented by formula (2) is 4-isopropylcyclohexanemethanol.
• the alicyclic alcohol composition of the present invention contains an alicyclic alcohol represented by the formula (1) and an alicyclic alcohol represented by the formula (2). These two components may be the only components constituting the alicyclic alcohol composition of the present invention. However, in reality, the alicyclic alcohol composition may contain by-products and raw materials generated during the production of the alicyclic alcohol composition. Therefore, the total content of the alicyclic alcohol represented by the formula (1) and the alicyclic alcohol represented by the formula (2) in the alicyclic alcohol composition of the present invention is preferably 95% by mass or more, more preferably 96% by mass or more, and even more preferably 97% by mass or more. There is no upper limit, and it is sufficient if it is 100% by mass or less, and the composition may consist only of the alicyclic alcohol represented by the formula (1) and the alicyclic alcohol represented by the formula (2).
• the mass ratio [(1)/(2)] of the alicyclic alcohol represented by the formula (1) and the alicyclic alcohol represented by the formula (2) in the alicyclic alcohol composition of the present invention is preferably 78/22 to 99/1, more preferably 78/22 to 95/5, and even more preferably 78/22 to 90/10 from the viewpoint of smoothness and softness of the lily of the valley fragrance, particularly from the viewpoint of the softness of the lingering fragrance, and from the viewpoint of improving the softness of the fragrance, still more preferably 83/17 to 90/10. Also, from the viewpoint of the softness of the lingering fragrance, particularly, it is still more preferably 83/17 to 95/5, and even more preferably 83/17 to 90/10.
• the alicyclic alcohol composition of the present invention is useful as a fragrance because it has a smooth and soft lily of the valley scent.
• the mass ratio of the alicyclic alcohol represented by the formula (1) and the alicyclic alcohol represented by the formula (2) within the above range the lily of the valley scent is intensified, resulting in a very smooth and soft lily of the valley scent, and the lingering scent is also soft, making it an excellent fragrance.
• the alicyclic alcohol composition when the alicyclic alcohol composition is incorporated into a fragrance composition, it can impart a very smooth and soft lily of the valley scent to the fragrance composition.
• An alicyclic alcohol composition containing an alicyclic alcohol represented by the following general formula (1) and an alicyclic alcohol represented by the following general formula (2) has a smooth and soft lily of the valley scent and can impart a smooth and soft lily of the valley scent to a fragrance composition, and therefore can be used as a fragrance.
• the above alicyclic alcohol composition has a particularly soft lingering scent and can be suitably used as a fragrance.
• the use of an alicyclic alcohol composition containing an alicyclic alcohol represented by the following general formula (1) and an alicyclic alcohol represented by the following general formula (2) as a fragrance is also included in the present invention.
• the compound represented by formula (1) is 3-isopropylcyclohexanemethanol.
• the compound represented by formula (2) is 4-isopropylcyclohexanemethanol.
• the mass ratio [(1)/(2)] of the alicyclic alcohol represented by formula (1) and the alicyclic alcohol represented by formula (2) in the alicyclic alcohol composition used as a fragrance is preferably 78/22 to 99/1, more preferably 78/22 to 95/5, and even more preferably 78/22 to 90/10 from the viewpoint of smoothness and softness of the lily of the valley fragrance, particularly from the viewpoint of the softness of the lingering fragrance, and is still more preferably 83/17 to 90/10 from the viewpoint of improving the softness of the fragrance. Also, particularly from the viewpoint of the softness of the lingering fragrance, it is still more preferably 83/17 to 95/5, and even more preferably 83/17 to 90/10.
• the alicyclic alcohol composition used as a fragrance has a smooth and soft lily of the valley scent and is therefore useful as a fragrance.
• the lingering scent is soft, making it useful as a fragrance.
• the mass ratio of the alicyclic alcohol represented by formula (1) and the alicyclic alcohol represented by formula (2) within the above range, the lily of the valley scent is intensified, resulting in a very smooth and soft lily of the valley scent, and the lingering scent is also soft, making it an excellent fragrance.
• it when incorporated into a fragrance composition, it will have a very smooth and soft lily of the valley scent.
• the fragrance composition of the present invention contains the alicyclic alcohol composition. That is, the fragrance composition of the present invention is a fragrance composition containing an alicyclic alcohol composition containing an alicyclic alcohol represented by the following formula (1) and an alicyclic alcohol represented by the following formula (2).
• the fragrance composition of the present invention contains the alicyclic alcohol composition as an active ingredient.
• the alicyclic alcohol composition can impart a smooth and soft lily of the valley scent to the fragrance composition.
• the fragrance composition of the present invention has the smooth and soft lily of the valley scent of the alicyclic alcohol composition, and is therefore useful as a fragrance component for various products.
• the mass ratio [(1)/(2)] of the alicyclic alcohol represented by the formula (1) and the alicyclic alcohol represented by the formula (2) in the alicyclic alcohol composition contained in the fragrance composition of the present invention is preferably 78/22 to 99/1, more preferably 78/22 to 95/5, and even more preferably 78/22 to 90/10 from the viewpoint of smoothness and softness of the lily of the valley fragrance, particularly from the viewpoint of the softness of the lingering fragrance, and from the viewpoint of improving the softness of the fragrance, still more preferably 83/17 to 90/10. Furthermore, from the viewpoint of the softness of the lingering fragrance, particularly, it is still more preferably 83/17 to 95/5, and even more preferably 83/17 to 90/10.
• the alicyclic alcohol composition contained in the fragrance composition of the present invention is useful as a fragrance because it has a smooth and soft lily of the valley scent.
• the mass ratio of the alicyclic alcohol represented by formula (1) and the alicyclic alcohol represented by formula (2) within the above range, the lily of the valley scent is intensified, and a very smooth and soft lily of the valley scent can be imparted to the fragrance composition.
• the content of the alicyclic alcohol composition in the fragrance composition of the present invention may be appropriately adjusted depending on the type of fragrance composition, the type of desired fragrance, the strength of the fragrance, etc., and is preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass, even more preferably 0.2 to 40% by mass, even more preferably 0.5 to 30% by mass, even more preferably 1 to 25% by mass, even more preferably 3 to 20% by mass, and even more preferably 4 to 15% by mass.
• fragrances other than the alicyclic alcohol represented by formula (1) or the alicyclic alcohol represented by formula (2), surfactants, solvents, antioxidants, colorants, etc. and at least one selected from the group consisting of fragrances other than the alicyclic alcohol represented by formula (1) or the alicyclic alcohol represented by formula (2), surfactants, solvents, antioxidants, and colorants is preferable, and at least one selected from the group consisting of fragrances other than the alicyclic alcohol represented by formula (1) or the alicyclic alcohol represented by formula (2), surfactants, solvents, antioxidants, and colorants is more preferable.
• the scent can be adjusted to suit the target product. Also, by including a solvent, it becomes easy to dissolve and impregnate the target product, and the strength and persistence of the scent can be adjusted.
• it is preferable to form a fragrance composition having at least one of a floral-like and a fruity-like scent by using a fragrance substance other than the alicyclic alcohol represented by formula (1) and the alicyclic alcohol represented by formula (2) it is more preferable to form a fragrance composition having a floral-like scent, and it is even more preferable to form a fragrance composition having both a floral-like and a fruity-like scent.
• the alicyclic alcohol composition is preferably contained as an active ingredient of a fragrance composition having at least one of a floral-like and a fruity-like scent, it is more preferable to contain it as an active ingredient of a fragrance composition having a floral-like scent, and it is even more preferable to contain it as an active ingredient of a fragrance composition having both a floral-like and a fruity-like scent.
• the fragrance other than the alicyclic alcohol represented by formula (1) or the alicyclic alcohol represented by formula (2) is not particularly limited as long as it is a conventionally known fragrance component, and a wide range of fragrances can be used.
• the following can be selected and used alone or in any mixture ratio of two or more:
• Fragrances other than the alicyclic alcohol represented by formula (1) or the alicyclic alcohol represented by formula (2) include hydrocarbons, alcohols, phenols, esters, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, natural essential oils, natural extracts, etc., and are preferably one or more fragrances selected from the group consisting of hydrocarbons, alcohols, phenols, esters, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, natural essential oils, and natural extracts.
• fragrances other than the alicyclic alcohol represented by formula (1) and the alicyclic alcohol represented by formula (2) are preferably at least one selected from the group consisting of aldehydes, natural essential oils, natural extracts, ethers, and esters, more preferably at least one selected from the group consisting of ethers and esters, and even more preferably esters.
• 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, and 1-(2-t-butylcyclohexyloxy)-2-butanol.
• the alcohols are alicyclic alcohols represented by formula (1) or alcohols other than alicyclic alcohols represented by formula (2).
• Examples of phenols include eugenol, thymol, and vanillin.
• Examples of esters include linalyl formate, citronellyl formate, geranyl formate, n-hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, terpinyl acetate, nopyr acetate, bornyl acetate, isobornyl acetate, o-t-butylcyclohexyl acetate, p-t-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styrallyl acetate, cinnamyl acetate, dimethylbenzylcarbinyl acetate, 3-pentyltetrahydropyran-4-yl acetate, citrone
• aldehydes examples include n-octanal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecenal, citronellal, citral, hydroxycitronellal, dimethyltetrahydrobenzaldehyde, 4(3)-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, 2-cyclohexylpropanal, p-t-butyl- ⁇ -methylhydrocinnamic aldehyde, p-isopropyl- ⁇ -methylhydrocinnamic aldehyde, p-ethyl- ⁇ , ⁇ -dimethylhydrocinnamic aldehyde, ⁇ -amylcinnamic aldehyde, ⁇ -hexylcinnamic aldehyde, piperonal, and ⁇ -methyl-3,4-methylenedioxyhydrocin
• 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 be polyoxyethylene alkyl sulfate ether, and polyoxyethylene lauryl sulfate ether is preferred.
• the fragrance composition containing the alicyclic alcohol composition can be used as a fragrance component for various products.
• products in which the fragrance composition can be used include fragrance products such as perfumes and colognes; hair cosmetics such as shampoos, conditioners, hair tonics, hair creams, mousses, gels, pomades, sprays, and other hair cosmetics; skin cosmetics such as lotions, beauty essences, creams, milky lotions, packs, foundations, face powders, lipsticks, and various types of make-up; dishwashing detergents, laundry detergents, softeners, disinfectant detergents, deodorizing detergents, indoor air fresheners, furniture care 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, etc.; and foods, etc.
• the blending amount of the fragrance composition in the above-mentioned product is not particularly limited, and the blending amount of the fragrance composition can be selected according to the type, properties, and sensory effect of the product to be scented.
• the blending amount of the fragrance composition in the product is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.001% by mass or more. Also, it is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 40% by mass or less.
• the amount of the fragrance composition in the product may be 80% by mass or more, or may be 100% by mass.
• Method for producing alicyclic alcohol composition Although there is no limitation on the method for producing the alicyclic alcohol composition containing the alicyclic alcohol represented by the formula (1) and the alicyclic alcohol represented by the formula (2), it is preferable to obtain the composition by the following production method.
• a preferred method for producing an alicyclic alcohol composition containing an alicyclic alcohol represented by the formula (1) and an alicyclic alcohol represented by the formula (2) includes a method of separately obtaining an alicyclic alcohol represented by the formula (1) and an alicyclic alcohol represented by the formula (2) and then mixing them in a desired ratio, and a method of hydrogenating an aromatic aldehyde represented by the following formula (3) and an aromatic aldehyde represented by the following formula (4) to obtain a mixture of an alicyclic alcohol represented by the following formula (1) and an alicyclic alcohol represented by the following formula (2).
• the aromatic aldehyde represented by formula (3) is 3-isopropylbenzaldehyde
• the aromatic aldehyde represented by formula (4) is 4-isopropylbenzaldehyde.
• the mass ratio [(3)/(4)] of the aromatic aldehyde represented by the formula (3) and the aromatic aldehyde represented by the formula (4) contained in the raw material of the present method is preferably 78/22 to 99/1, more preferably 78/22 to 95/5, and even more preferably 78/22 to 90/10 from the viewpoint of smoothness and softness of the lily of the valley fragrance, particularly from the viewpoint of the softness of the lingering fragrance, and is even more preferably 83/17 to 90/10 from the viewpoint of improving the softness of the fragrance.
• the mass ratio of the aromatic aldehyde represented by formula (3) and the aromatic aldehyde represented by formula (4) is within the above range, it is possible to obtain an alicyclic alcohol composition having a desired desirable fragrance.
• the hydrogenation method is not particularly limited, and can be carried out by a known method using a hydrogenation catalyst.
• the hydrogenation catalyst is not particularly limited, and any known catalyst can be used.
• the hydrogenation catalyst is preferably a supported heterogeneous hydrogenation catalyst, a Ziegler type hydrogenation catalyst, a homogeneous hydrogenation catalyst, or a sponge metal catalyst.
• the supported heterogeneous hydrogenation catalyst is a catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like.
• the Ziegler type hydrogenation catalyst uses a transition metal salt and a reducing agent such as organoaluminum, etc.
• transition metal salt examples include organic acid salts or acetylacetone salts of Ni, Co, Fe, Cr, etc.
• examples of the homogeneous hydrogenation catalyst include organometallic compounds of Ti, Ru, Rh, Zr, etc.
• sponge metal catalyst examples include sponge metal catalysts such as sponge nickel and sponge cobalt.
• the temperature of the hydrogenation reaction in this step is, from the viewpoints of suppressing reactivity and side reactions, preferably 0° C. or higher, more preferably 10° C. or higher, even more preferably 20° C. or higher, and preferably 150° C. or lower, even more preferably 120° C. or lower.
• the pressure of hydrogen used in the hydrogenation reaction is preferably 0.01 MPaG or more, more preferably 0.03 MPaG or more, even more preferably 0.05 MPaG or more, and preferably 10 MPaG or less, more preferably 3 MPaG or less, even more preferably 1 MPaG or less, and still more preferably 0.5 MPaG or less.
• the reaction time is not particularly limited, but is preferably 3 minutes or more, more preferably 10 minutes or more, even more preferably 30 minutes or more, and is preferably 24 hours or less, more preferably 12 hours or less, even more preferably 8 hours or less.
• the hydrogenation reaction may be carried out in the presence of a solvent.
• the solvent to be used is not particularly limited as long as it does not inhibit the hydrogenation reaction, but is preferably a hydrocarbon solvent, and more preferably at least one selected from the group consisting of aliphatic hydrocarbons and alicyclic hydrocarbons.
• the aliphatic hydrocarbon include pentane, hexane, isopentane, heptane, octane, and isooctane.
• the alicyclic hydrocarbon include cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc. These may be used alone or in combination of two or more.
• the method for purifying the target alicyclic alcohol composition or each alicyclic alcohol from the solution after the reaction is completed is not particularly limited, and a publicly known method may be appropriately selected and carried out. Specific examples include filtration, chromatography, distillation purification, etc., and the target alicyclic alcohol composition or each alicyclic alcohol with a high purity can be obtained by purifying using an appropriate combination of these. If each alicyclic alcohol is produced separately, it is possible to obtain the alicyclic alcohol composition by mixing them afterwards.
• the oven was heated to 280° C. at 10° C./min and held there for 7 minutes. The oven was then heated to 300° C. at 10° C./min and held there for 5 minutes.
• ⁇ GC-MS analysis method (compound structure)> The products obtained in the Production Examples and Examples were subjected to GC-MS analysis under the following conditions.
• Equipment used Gas chromatograph GC2010 Plus (Shimadzu Corporation) Column: DB-1MS (length 30 m, inner diameter 0.25 mm, film thickness 0.25 ⁇ m)
• Injection volume 1 ⁇ L
• Carrier gas He Linear velocity control: 38.0 cm/s Split ratio: 28.1 Oven temperature: The oven was heated from 50° C. to 150° C. at 5° C./min, and after reaching 150° C., the oven was heated to 280° C. at 10° C./min and held there for 7 minutes.
• fragrance and fragrance tone of the alicyclic alcohols, alicyclic alcohol compositions, and fragrance compositions of the Examples and Comparative Examples were evaluated by impregnating them into filter paper 8 mm wide and 15 cm long, and having a professional panel smell them. Specific evaluation criteria, etc. are shown in the evaluation results of each Example and Comparative Example.
• Example 1 (Production of 3-isopropylcyclohexanemethanol) 3-Isopropylbenzaldehyde (Fluorochem, 15 g), t-butyl alcohol (FUJIFILM Wako Pure Chemical Industries, Ltd., 160 g), and 5% ruthenium-alumina catalyst (NE Chem-Cat, dry product, powder type, 5 g) were charged into a 500 mL stainless steel autoclave, and the atmosphere inside the reactor was replaced with nitrogen and hydrogen. Then, hydrogen was introduced so that the hydrogen pressure became 8.0 MPa, and a hydrogenation reaction was carried out with stirring at a reaction temperature of 80° C. for 6 hours.
• NE Chem-Cat dry product, powder type, 5 g
• the reaction liquid was filtered to remove the catalyst, and then the t-butyl alcohol was removed by simple distillation to obtain a crude composition.
• the resulting crude composition was rectified at 10 torr using a rectification column having 40 theoretical plates, and 3-isopropylcyclohexanemethanol (alicyclic alcohol represented by formula (1)) was obtained as a fraction having a distillation temperature of 113°C.
• the analytical results of 3-isopropylcyclohexanemethanol are shown below.
• Example 1 The aroma and fragrance tone of the 3-isopropylcyclohexanemethanol obtained in Example 1 was evaluated. The results are shown in Table 1. Furthermore, the aroma and fragrance tone of the 4-isopropylcyclohexanemethanol obtained in Production Example 1 as Comparative Example 1 and FLOROL (isobutylmethyltetrahydropyranol) as Comparative Example 2 were also evaluated. The results are shown in Table 1. The fragrance and fragrance tone evaluation was also performed based on Comparative Example 1. In addition, the natural feeling, lingering fragrance, diffusibility, and alcohol odor were also evaluated.
• fragrances and fragrance compositions having the scent of lily of the valley are preferred as components of fragrances and fragrance compositions having the scent of lily of the valley, and those not having an alcohol odor are preferred as components of fragrances and fragrance compositions having the scent of lily of the valley.
• the fragrance evaluation was made by comprehensively judging the above evaluation results according to the following criteria: The more natural the fragrance, the longer it lingers, and the more diffusible it is, the better the fragrance is.
• B Has a natural feel, but has no lingering or diffusibility.
• C The natural feeling is weak (similar to Comparative Example 1).
• D Does not have a natural feel.
• the alicyclic alcohol of Example 1 had a smooth, clean, natural lily of the valley scent. It also had excellent fragrance diffusion and lingering properties. Therefore, the alicyclic alcohol of Example 1 can be used as a fragrance.
• Example 2 and Comparative Examples 3 to 4 Green, floral, fruity fragrance compositions
• 3-isopropylcyclohexanemethanol (alicyclic alcohol represented by formula (1)) obtained in Example 1 was added to the blended fragrance base (green floral fruity fragrance composition) shown in Table 2 at 5% by mass, and the fragrance and fragrance tone were evaluated.
• FLOROL isobutylmethyltetrahydropyranol
• Comparative Example 4 the amount of dipropylene glycol in the blended fragrance base shown in Table 2 was changed from 21.73% by mass to 26.73% by mass, and the fragrance and fragrance tone were evaluated.
• the fragrance and fragrance tone were also evaluated in terms of natural feeling, woody odor, and alcohol odor.
• a fragrance composition having a natural feeling is preferable as a green floral fruity fragrance composition, and a fragrance composition having no woody odor or alcohol odor is preferable as a green floral fruity fragrance composition.
• the fragrance composition of Example 2 had no rough tones, a clear and natural lily of the valley note, and a stronger clean green floral scent than the fragrance composition of the comparative example. Furthermore, it had a very natural, clear, and deep, fresh floral feeling of lily of the valley (the image of a petal).
• Example 3 and Comparative Examples 5 to 6 (Marine, floral, fruity fragrance compositions)
• 3-isopropylcyclohexanemethanol alicyclic alcohol represented by formula (1)
• Example 1 3-isopropylcyclohexanemethanol (alicyclic alcohol represented by formula (1)) obtained in Example 1 was added to the blended fragrance base (marine, floral, fruity fragrance composition) shown in Table 3 at 10% by mass, and the fragrance and fragrance tone were evaluated.
• FLOROL isobutylmethyltetrahydropyranol
• Comparative Example 6 the amount of dipropylene glycol in the blended fragrance base shown in Table 3 was changed from 11.82% by mass to 21.82% by mass, and the fragrance and fragrance tone were evaluated.
• fragrance and fragrance tone were also evaluated in terms of natural feeling, woody odor, and alcohol odor.
• a fragrance composition having a natural feeling is preferable as a marine, floral, fruity fragrance composition, and a fragrance composition having no woody odor or alcohol odor is preferable as a marine, floral, fruity fragrance composition.
• the fragrance composition of Example 3 had a clear, natural lily of the valley note and a clean, green floral scent compared to the fragrance composition of the comparative example, without any rough tones. Furthermore, it had a bright, naturally sweet lily of the valley scent that was highly palatable.
• the alicyclic alcohol composition of the example was very smooth and soft, and had a lily of the valley scent.Furthermore, the alicyclic alcohol composition of the example had a soft after-scent.Therefore, the alicyclic alcohol composition of the example can be used as a fragrance, and can also be suitably used as an active ingredient of a fragrance composition.

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