Alicyclic alcohol, alicyclic alcohol composition, and fragrance composition

Abstract

An alicyclic alcohol represented by formula (1).

Description

[Technical Field]

[0001] The present invention relates to an alicyclic alcohol, a method for producing the same, an alicyclic alcohol composition containing the alicyclic alcohol, and a fragrance composition. [Background technology]

[0002] It is known that some alicyclic alcohols are useful as raw materials for compounded fragrances. For example, Non-Patent Document 1 describes that p-isopropylcyclohexylmethanol (Mayol), which has a floral scent, p-isopropylcyclohexanol, which has a floral scent of lilac, rose, geranium, and mint, and 2,4-dimethyl-3-cyclohexene-1-methanol, which has a fresh, green, floral scent reminiscent of hyacinth and lily of the valley, are useful as raw materials for compounded fragrances, and describes their use in skin care products, etc.

[0003] Furthermore, Patent Document 1 discloses an alicyclic alcohol compound having an excellent, refreshing, and fresh floral-green fragrance. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Genichi Indo, "Revised and Expanded Edition of Synthetic Fragrances: Chemistry and Product Knowledge," 1996, pp. 54-56, Chemical Daily Press [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-140353 Summary of the Invention [Problem to be solved by the invention]

[0006] Alicyclic alcohols used as fragrances are used in a variety of fields, including cosmetics including skin care products as described above, as well as fragrance products, detergents, miscellaneous goods, pharmaceuticals, foods, etc. In order to increase the value of products, new scents are being developed, and fragrances with novel scents are in demand. Therefore, an object of the present invention is to provide an alicyclic alcohol which has a complex fragrance containing the floral fragrance and lingering scent of lily of the valley, jasmine, and rose, as well as a soft woody fragrance, has excellent lingering properties, and can impart diffusibility to the floral and woody fragrances in blended fragrances, and is useful as a fragrance and also as a raw material for blended fragrances. [Means for solving the problem]

[0007] The present inventors synthesized and blended various alicyclic alcohols and compositions containing a plurality of these alcohols, and evaluated their fragrances. As a result, they found that specific alicyclic alcohols and compositions containing them have excellent fragrance notes and are also excellent as raw materials for blended fragrances, which led to the completion of the present invention.

[0008] That is, the present invention is as follows. [1] An alicyclic alcohol represented by the following formula (1): [ka] [2] A fragrance composition containing the alicyclic alcohol described in [1] above. [3] An alicyclic alcohol composition containing an alicyclic alcohol represented by the following formula (1) and an alicyclic alcohol represented by the following formula (2): [ka] [4] The alicyclic alcohol composition according to [3] above, further comprising an alicyclic alcohol represented by the following formula (3): [ka] [5] The alicyclic alcohol composition according to [3] or [4] above, wherein the total content of the alicyclic alcohol represented by the formula (1) and the alicyclic alcohol represented by the formula (2) is 95% by mass or more. [6] The alicyclic alcohol composition according to any one of the above [3] to [5], wherein the content of the alicyclic alcohol represented by the formula (1) is 85% by mass or more and 98% by mass or less. [7] The alicyclic alcohol composition according to any one of the above [3] to [6], wherein the mass ratio [(1) / (2)] of the alicyclic alcohol represented by the formula (1) to the alicyclic alcohol represented by the formula (2) in the alicyclic alcohol composition is 85 / 15 to 98 / 2. [8] A fragrance composition containing the alicyclic alcohol composition according to any one of the above [3] to [7]. [9] An alicyclic alcohol represented by the following formula (2): [ka]

[10] A fragrance composition containing the alicyclic alcohol described in [9] above.

[11] A method for producing an alicyclic alcohol, comprising hydrogenating an aromatic aldehyde represented by the following general formula (4) to obtain an alicyclic alcohol represented by the following general formula (5): [ka] [Effects of the Invention]

[0009] According to the present invention, an alicyclic alcohol can be provided which has a complex fragrance that includes the floral fragrance and lingering scent of lily of the valley, jasmine, and rose, as well as a soft woody fragrance, and has excellent lingering properties, making it useful as a fragrance, and furthermore, can impart diffusibility to the floral and woody fragrances in blended fragrances, making it useful as a raw material for blended fragrances. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Alicyclic alcohol represented by formula (1)] The alicyclic alcohol represented by the following formula (1) of the present invention is (4-isopropyl-2-methylcyclohexyl)methanol. [ka]

[0011] The alicyclic alcohol represented by formula (1) is useful as a fragrance because it has a complex fragrance that includes the floral and woody notes of lily of the valley, jasmine, and rose, and a soft woody note with excellent lingering properties. Furthermore, it is useful as a raw material for blended fragrances because it can impart diffusibility to the floral and woody notes in blended fragrances. The alicyclic alcohol represented by formula (1) is preferably obtained by the production method described below. [Alicyclic alcohol composition] The alicyclic alcohol composition of the present invention contains an alicyclic alcohol represented by the following formula (1) and an alicyclic alcohol represented by the following formula (2): The alicyclic alcohol represented by the following formula (1) is the aforementioned (4-isopropyl-2-methylcyclohexyl)methanol. [ka]

[0012] <Alicyclic alcohol represented by formula (2)> The alicyclic alcohol represented by formula (2) contained in the alicyclic alcohol composition of the present invention is (2-isopropyl-4-methylcyclohexyl)methanol. The alicyclic alcohol represented by formula (2) is also useful as a fragrance.

[0013] <Composition of the Alicyclic Alcohol Composition> 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, as long as it is 100% by mass or less.

[0014] The content of the alicyclic alcohol represented by the formula (1) in the alicyclic alcohol composition of the present invention is preferably 85% by mass or more, more preferably 87% by mass or more, even more preferably 90% by mass or more, and is preferably 98% by mass or less, more preferably 97% by mass or less, even more preferably 95% by mass or less. The content of the alicyclic alcohol represented by the formula (2) in the alicyclic alcohol composition of the present invention is preferably 2% by mass or more, more preferably 5% by mass or more, and is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 10% by mass or less.

[0015] In the alicyclic alcohol composition of the present invention, the mass ratio [(1) / (2)] of the alicyclic alcohol represented by the formula (1) to the alicyclic alcohol represented by the formula (2) is preferably 85 / 15 to 98 / 2, more preferably 87 / 13 to 97 / 3, even more preferably 87 / 13 to 95 / 5, and still more preferably 90 / 10 to 95 / 5.

[0016] The alicyclic alcohol composition of the present invention may further contain an alicyclic alcohol represented by the following formula (3): [ka]

[0017] When the alicyclic alcohol composition of the present invention contains an alicyclic alcohol represented by the formula (3), the content of the alicyclic alcohol represented by the formula (3) in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and is preferably 3% by mass or less, more preferably 2% by mass or less.

[0018] The alicyclic alcohol composition of the present invention having the above-mentioned composition has a floral fragrance of lily of the valley, jasmine, and rose, with a woody fragrance remaining, and is useful as a fragrance. It is also useful as a raw material for blended fragrances (fragrance compositions), and can be used as a fragrance component for various products.

[0019] [Fragrance composition] The fragrance composition of the present invention contains the alicyclic alcohol or the alicyclic alcohol composition. That is, the fragrance composition of the first embodiment of the present invention contains an alicyclic alcohol represented by the following formula (1): [ka]

[0020] The content of the alicyclic alcohol in the fragrance composition of the present invention may be adjusted as appropriate depending on the type of fragrance composition, the type and intensity of the desired fragrance, etc., and is preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass. Furthermore, the fragrance composition of the second embodiment of the present invention contains an alicyclic alcohol composition containing an alicyclic alcohol represented by the following formula (1) and an alicyclic alcohol represented by the following formula (2): [ka]

[0021] In the fragrance composition of the second embodiment of the present invention, the mass ratio [(1) / (2)] of the alicyclic alcohol represented by the formula (1) to the alicyclic alcohol represented by the formula (2) is preferably 85 / 15 to 98 / 2, more preferably 87 / 13 to 97 / 3, even more preferably 87 / 13 to 95 / 5, and still more preferably 90 / 10 to 95 / 5.

[0022] Furthermore, the fragrance composition of the second embodiment of the present invention may further contain an alicyclic alcohol represented by the following formula (3): [ka]

[0023] 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 and intensity of the desired fragrance, etc., and is preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass.

[0024] In the fragrance composition of the present invention, fragrance components that can be used in combination with the alicyclic alcohol or the alicyclic alcohol composition include, but are not limited to, surfactants such as polyoxyethylene lauryl sulfate ether; solvents such as dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, and triethyl citrate; hydrocarbons such as limonene, α-pinene, β-pinene, terpinene, cedrene, longifolene, and valencene; linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenol, ethyl linalool, farnesol, nerolidol, cis-3-hexenol, menthol, borneol, and β-phenylenediamine. Alcohols such as ethyl alcohol, benzyl alcohol, phenylhexanol, 2,2,6-trimethylcyclohexyl-3-hexanol, 1-(2-t-butylcyclohexyloxy)-2-butanol, 4-isopropylcyclohexanemethanol, 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 such as eugenol, thymol, and vanillin;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, ot-butylcyclohexyl acetate, pt-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styrallyl acetate, cinnamyl acetate, dimethicone benzyl carbinyl acetate, 3-pentyltetrahydropyran-4-yl acetate, citronellyl propionate, tricyclodecenyl propionate, allyl cyclohexyl propionate, ethyl 2-cyclohexyl propionate, benzyl propionate, citronellyl butyrate, dimethyl benzyl carbinyl n-butyrate, tricyclodecenyl isobutyrate, methyl 2-nonenoate, methyl benzoate, benzyl benzoate, methyl cinnamate, methyl salicylate, n-hexyl Esters such as methyl salicylate, cis-3-hexenyl salicylate, geranyl tiglate, cis-3-hexenyl tiglate, methyl jasmonate, methyl dihydrojasmonate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, ethyl methylphenylglycidate, methyl anthranilate, and fultate; n-octanal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecenal, citronellal, citral, and dimethyltetrahydrobenzaldehyde. aldehydes such as 4(3)-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, 2-cyclohexylpropanal, pt-butyl-α-methylhydrocinnamic aldehyde, p-isopropyl-α-methylhydrocinnamic aldehyde, p-ethyl-α,α-dimethylhydrocinnamic aldehyde, α-amylcinnamic aldehyde, α-hexylcinnamic aldehyde, piperonal, and α-methyl-3,4-methylenedioxyhydrocinnamic aldehyde;Methylheptenone, 4-methylene-3,5,6,6-tetramethyl-2-heptanone, amylcyclopentanone, 3-methyl-2-(cis-2-penten-1-yl)-2-cyclopenten-1-one, methylcyclopentenolone, rose ketone, γ-methylionone, α-ionone, carvone, menthone, camphor, nootkatone, benzylacetone, anisylacetone, methyl β-naphthyl ketone, 2,5-dimethyl-4-hydroxy-3(2H)-furan Ketones such as methylnaphthalene, 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 such as acetaldehyde ethyl phenylpropyl acetal, citral diethyl acetal, phenylacetaldehyde glycerin acetal, and ethyl acetoacetate ethylene glycol ketal; and anethole. Ethers such as β-naphthyl methyl ether, β-naphthyl ethyl ether, limonene oxide, rose oxide, 1,8-cineole, racemic or optically active dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan; nitriles such as citronellyl nitrile; γ-nonalactone, γ-undecalactone, σ-decalactone, γ-jasmolactone, coumarin, cyclopentadecanolide, cyclohexadecanolide, ambroxanthate, etc. lactones such as ethylene brassylate, 11-oxahexadecanolide, etc.; and other fragrance substances such as natural essential oils and natural extracts of orange, lemon, bergamot, mandarin, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, geranium, jasmine, ylang-ylang, anise, clove, ginger, nutmeg, cardamom, cedar, cypress, vetiver, patchouli, labdanum, etc. These other fragrance substances may be used alone or in combination.

[0025] The fragrance composition of the present invention can be used as a fragrance component in various products such as cosmetics, health and hygiene materials, miscellaneous goods, beverages, foods, quasi-drugs, and pharmaceuticals in order to impart fragrance and improve the fragrance of the products to which it is blended. The fragrance composition of the present invention can be used as an aroma component for, for example, fragrance products such as perfumes and colognes; hair cosmetics such as shampoos, conditioners, hair tonics, hair creams, mousses, gels, pomades, and sprays; skin cosmetics such as lotions, serums, creams, emulsions, packs, foundations, face powders, lipsticks, and makeup cosmetics; hygiene products such as dishwashing detergents, laundry detergents, household detergents, glass cleaners, fabric softeners, bleaches, air fresheners, and insecticides; quasi-drugs such as toothpastes, mouthwashes, bath additives, antiperspirants, and perm agents; miscellaneous goods such as paper products; pharmaceuticals; and foods.

[0026] The content of the fragrance composition of the present invention in the above products may be adjusted appropriately depending on the fragrance strength required for each product, and is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass.

[0027] The fragrance composition of the third embodiment of the present invention contains an alicyclic alcohol represented by the formula (2). The alicyclic alcohol represented by the formula (2) is also useful as a raw material for blended fragrances (fragrance compositions), and the content of the alicyclic alcohol represented by the formula (2) in the fragrance composition is preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass. Examples of fragrance components that can be used in combination with each alicyclic alcohol include those listed above. Furthermore, the content of the fragrance composition in each of these products is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass.

[0028] [Method for producing alicyclic alcohol and method for producing alicyclic alcohol composition] The alicyclic alcohol constituting the alicyclic alcohol composition of the present invention may be obtained by any production method, but is preferably obtained by a production method in which an aromatic aldehyde represented by the following general formula (4) is hydrogenated to obtain an alicyclic alcohol represented by the following general formula (5): [ka]

[0029] Here, the aromatic aldehyde represented by general formula (4) includes aromatic aldehydes represented by the following formula (4-1), aromatic aldehydes represented by the following formula (4-2), and aromatic aldehydes represented by the following formula (4-3). [ka] According to this production method, an alicyclic alcohol represented by formula (1) can be obtained from an aromatic aldehyde represented by formula (4-1), an alicyclic alcohol represented by formula (2) can be obtained from an aromatic aldehyde represented by formula (4-2), and an alicyclic alcohol represented by formula (3) can be obtained from an aromatic aldehyde represented by formula (4-3). The alicyclic alcohol composition of the present invention contains an alicyclic alcohol represented by formula (1) and an alicyclic alcohol represented by formula (2). The composition may be obtained directly by hydrogenating a mixture of aromatic aldehyde represented by formula (4-1) and aromatic aldehyde represented by formula (4-2) as raw materials, or the respective alicyclic alcohols may be obtained and then mixed to obtain the composition.

[0030] The alicyclic alcohol represented by the general formula (5) includes the alicyclic alcohol represented by the formula (1), the alicyclic alcohol represented by the formula (2), and the alicyclic alcohol represented by the formula (3).

[0031] The aromatic aldehyde represented by general formula (4), which is the raw material for the hydrogenation reaction, may be obtained by any method, but is preferably synthesized by formylation of cymene (isopropyltoluene) using a super strong acid, as shown in the following formula: [ka] Formylation to obtain the aromatic aldehyde represented by formula (4) used in the production method of the present invention is preferably carried out by reacting cymene with carbon monoxide in the presence of a super strong acid, and more specifically, by reacting cymene with carbon monoxide in the presence of a Bronsted acid such as HF / BF and a Lewis acid. When HF / BF3 is used as the Bronsted acid and the Lewis acid, the amount of HF used is preferably 5 to 25 times by mole relative to the raw material cymene, and the amount of BF3 used is preferably 0.2 to 2.5 times by mole relative to the raw material cymene. The reaction temperature is preferably -30 to 10°C. The reaction is preferably carried out under pressure, and the reaction pressure is preferably 1.0 to 3.0 MPaG. The reaction time is preferably 0.2 to 5 hours.

[0032] By using m-cymene as the starting material, the aromatic aldehyde represented by formula (4-1) can be obtained in high yield. However, by formylation under the above reaction conditions, the aromatic aldehyde represented by formula (4-1) can also be obtained in high yield from p-cymene. When formylation is carried out using p-cymene, the aromatic aldehyde represented by the formula (4-2) is obtained as a by-product. Therefore, by using p-cymene as a raw material, an aromatic aldehyde mixture containing the aromatic aldehyde represented by the formula (4-1) and the aromatic aldehyde represented by the formula (4-2), which is the raw material for the alicyclic alcohol composition of the present invention, can be obtained. Since p-cymene is available at a lower cost than m-cymene, it is preferable to formylate p-cymene or a mixture of p-cymene and m-cymene to obtain an aromatic aldehyde mixture in which the main product is the aromatic aldehyde represented by formula (4-1), and then distill this to obtain a high-purity aromatic aldehyde represented by formula (4-1), which is a raw material for the alicyclic alcohol represented by formula (1). It is also preferable to formylate p-cymene or a mixture of p-cymene and m-cymene to obtain an aromatic aldehyde mixture containing an aromatic aldehyde represented by formula (4-1) and an aromatic aldehyde represented by formula (4-2), and use the resulting mixture as is as a raw material for an alicyclic alcohol composition containing an alicyclic alcohol represented by formula (1) and an alicyclic alcohol represented by formula (2).

[0033] The ratio of the aromatic aldehyde mixture can be adjusted by adjusting the ratio of the raw materials m-cymene and p-cymene or by adjusting the conditions of the formylation reaction using p-cymene. The ratio can also be adjusted by distilling the resulting aromatic aldehyde mixture. In this way, an aromatic aldehyde mixture containing the aromatic aldehyde represented by formula (4-1) and the aromatic aldehyde represented by formula (4-2) in any ratio can be obtained. In addition, the aromatic aldehyde represented by formula (4-3) is contained as a by-product. The aromatic aldehyde or aromatic aldehyde mixture thus obtained may be used as is in the hydrogenation reaction, but may be further purified to increase the purity of the target aromatic aldehyde or to adjust the ratio to a desired level.

[0034] The reaction conditions for the hydrogenation reaction in the production method of the present invention are not particularly limited, but it is preferable to place the aromatic aldehyde or aromatic aldehyde mixture, the hydrogenation catalyst, and, if necessary, a solvent, etc., in a pressure vessel and then introduce hydrogen. The hydrogenation catalyst used in this reaction may be any metal catalyst commonly used in hydrogenation, and specific examples thereof include ruthenium catalysts, palladium catalysts, platinum catalysts, cobalt catalysts, and nickel catalysts. From the viewpoint of being able to simultaneously hydrogenate an aromatic ring and an aldehyde group, the hydrogenation catalyst is preferably at least one selected from the group consisting of ruthenium catalysts, palladium catalysts, and platinum catalysts, and more preferably a ruthenium catalyst. Examples of the carrier for the metal catalyst include activated carbon, alumina, and diatomaceous earth, with activated carbon being preferred. In this reaction, a solvent may be used, and it is preferable to use a solvent that does not affect the hydrogenation reaction of the alicyclic hydrocarbon compound and the saturated aliphatic hydrocarbon compound. It is preferable to use substantially no solvent, since this eliminates the need for a solvent removal step.

[0035] The hydrogen used in this reaction does not need to be particularly purified and may be of industrial grade. The hydrogen pressure during the reaction is preferably 2.0 to 20.0 MPa, more preferably 3.0 to 15.0 MPa, and even more preferably 5.0 to 10.0 MPa. The reaction temperature is preferably 80 to 150° C., more preferably 110 to 140° C. This range is preferable because hydrogenolysis of the hydroxy group can be suppressed and the target product can be obtained in high yield. In the hydrogenation reaction, the aromatic ring and the aldehyde group are preferably hydrogenated simultaneously to obtain the target alicyclic alcohol or alicyclic alcohol composition in one pot; however, the reaction may be carried out in two stages so that the aromatic ring and the aldehyde group are hydrogenated separately. The alicyclic alcohol or alicyclic alcohol composition thus obtained is preferably purified by distillation, and the distillation conditions may be appropriately adjusted by adjusting the pressure and temperature during distillation.

[0036] In this way, an alicyclic alcohol composition containing an alicyclic alcohol represented by formula (1), an alicyclic alcohol represented by formula (2), or both an alicyclic alcohol represented by formula (1) and an alicyclic alcohol represented by formula (2) can be obtained. Each of these can be used as a fragrance, or they can be mixed in any ratio. In particular, it is preferable to use an alicyclic alcohol composition containing an alicyclic alcohol represented by formula (1) and an alicyclic alcohol represented by formula (2) in the above-mentioned ratio. The obtained alicyclic alcohol represented by the formula (1) has a complex fragrance containing floral fragrances of mugwort, jasmine, and rose and a soft woody fragrance in the residual fragrance, is useful as a fragrance, and can further impart residual fragrance and diffusibility to compounded fragrances. Therefore, it is also useful as a raw material for compounded fragrances (fragrance compositions). The alicyclic alcohol represented by the formula (2) is also useful as a fragrance. Further, an alicyclic alcohol composition containing both the alicyclic alcohol represented by the formula (1) and the alicyclic alcohol represented by the formula (2) has a fragrance containing floral fragrances of mugwort, jasmine, and rose and a woody fragrance in the residual fragrance and is useful as a fragrance.

Examples

[0037] The present invention will be specifically described based on the examples shown below, but the present invention is not limited by these examples.

[0038] <Gas chromatography analysis method (composition ratio)> The composition ratios of the products obtained in the production examples and examples were determined by gas chromatography under the following conditions. Equipment used: Gas chromatography Nexis GC-2030 (manufactured by Shimadzu Corporation) Column: DB-1 (length 30 m, inner diameter 0.53 mm, film thickness 1.5 μm) Detector: FID (H2 30 mL / min, Air 300 mL / min) Carrier gas: He (constant flow; average linear velocity 38 cm / sec) Split ratio: 28.1 Inlet temperature: 300 °C Detector temperature: 300 °C Injection volume: 1.0 μL Oven temperature: The temperature was raised from 50 °C to 150 °C at 5 °C / min, and after reaching 150 °C, the temperature was raised to 280 °C at 10 °C / min and then held for 7 minutes. Thereafter, the temperature was raised to 300 °C at 10 °C / min and held for 5 minutes.

[0039] <NMR analysis method (structure of compound)> GC-MS analysis was performed on the alicyclic alcohol obtained in Example 2 under the following conditions. Equipment used: Varian NMR System PS600 600MHz NMR spectrometer Resonance frequency: 600MHz Measurement temperature: Room temperature Measurement range: -2 ≤ δ ≤ 14 Solvent: CDCl3 Chemical shift reference substance: CHCl3 in CDCl3 (δ = 7.26)

[0040] <GC-MS analysis method (structure of compound)> GC-MS analysis was performed on the alicyclic alcohol obtained in Example 2 under the following conditions. (GC side) Equipment used: Gas chromatography GC2010 Plus (manufactured by Shimadzu Corporation) Column: DB-1MS (length 30m, inner diameter 0.25mm, film thickness 0.25μm) Injection volume: 1μL Vaporization chamber temperature: 300°C Carrier gas: He Linear velocity control: 38.0cm / s Split ratio: 28.1 Oven temperature: It was heated from 50°C to 150°C at a rate of 5°C / min, and after reaching 150°C, it was heated to 280°C at a rate of 10°C / min and then held for 7 minutes. Then it was heated to 300°C at a rate of 10°C / min and held for 5 minutes. (MS side) Equipment used: GCMS-QP2010 Ultra (manufactured by Shimadzu Corporation) Fragmentation method: EI Ion source temperature: 200°C Interface temperature: 250°C Detector voltage: 0.8kV

[0041] Production Example 1 (Production of aromatic aldehyde mixture) A 500 mL autoclave equipped with a drive-type stirrer, three inlet nozzles at the top, and one outlet nozzle at the bottom, and capable of controlling the internal temperature via a jacket, was used as the formylation reactor. A coolant was passed through the jacket, and the autoclave was cooled to -25°C. 126.5 g (6.32 mol) of hydrogen fluoride was then charged. While stirring, 42.6 g (0.63 mol) of boron trifluoride was then added, while maintaining the temperature below -25°C. After the boron trifluoride addition, the pressure inside the autoclave was increased to 2 MPaG with carbon monoxide while maintaining the temperature at -25°C, and 56.7 g (0.42 mol) of m,p-mixed cymene (isopropyl toluene, m:p (molar ratio) = 68.3:31.7) was added. After stirring for 45 minutes while maintaining a temperature of -25°C and a pressure of 2 MPaG, the reaction mixture in the autoclave was drained into ice water. The drained mixture was shaken well and the oil layer was separated. The resulting oil layer was washed with water to obtain a crude aromatic aldehyde mixture. The obtained crude aromatic aldehyde mixture was subjected to removal of low boiling point components using a distillation column with 20 theoretical plates. The distillation column pressure was set to 15 torr, and low boiling point components were distilled off until the distillation temperature reached 126°C. Once the distillation temperature reached 126°C, fractions were collected to obtain an aromatic aldehyde mixture containing 4-isopropyl-2-methylbenzaldehyde (formula (4-1)), 2-isopropyl-4-methylbenzaldehyde (formula (4-2)), and 5-isopropyl-2-methylbenzaldehyde (formula (4-3)) in a mass ratio of 91:7:2.

[0042] Example 1 (Production of alicyclic alcohol composition) The aromatic aldehyde mixture obtained in Production Example 1 was subjected to a hydrogenation reaction. 150.0 g of an aromatic aldehyde mixture and 16.5 g (dry weight 7.5 g) of a 5% by mass Ru / C catalyst with a water content of 54.7% were charged into a 500 mL autoclave, and after replacing the atmosphere in the reactor with nitrogen and hydrogen, hydrogen was introduced to a hydrogen pressure of 8.0 MPa. The reaction was carried out for 6 hours with stirring at a reaction temperature of 140°C to obtain an alicyclic alcohol composition. The reaction endpoint was the point at which hydrogen consumption was completed. The obtained alicyclic alcohol composition was an alicyclic alcohol composition containing (4-isopropyl-2-methylcyclohexyl)methanol (formula (1)), (2-isopropyl-4-methylcyclohexyl)methanol (formula (2)), and (5-isopropyl-2-methylcyclohexyl)methanol (formula (3)) in a mass ratio of 91:7:2. The resulting alicyclic alcohol composition had a floral fragrance of lily of the valley, jasmine, and rose, with a woody fragrance as a lingering scent.

[0043] Example 2 (Production of alicyclic alcohol) First, an alicyclic alcohol composition was obtained in the same manner as in Example 1. The obtained alicyclic alcohol composition was subjected to rectification using a rectification column with 200 theoretical plates (distillation temperature 121°C, vacuum degree 10 torr) to obtain the alicyclic alcohol (4-isopropyl-2-methylcyclohexyl)methanol (formula (1)) with a purity of 98.5% by mass. The resulting alicyclic alcohol had a complex fragrance containing floral notes of lily of the valley, jasmine, and rose, with a soft woody scent like sandalwood remaining.

[0044] The analytical results for the alicyclic alcohol (4-isopropyl-2-methylcyclohexyl)methanol (formula (1)) are shown below.

[0045] (NMR analysis results) 1 H NMR (600 MHz, CDCl3) δ 2H 3.72 (dd, J=4.8 and 10.8 Hz), 3.59 (dd, J=9.9 Hz), 3.42~3.52 (m); 1H 2.05~2.15(m), 1.97 (dq, J=3.2 and 13.5 Hz), 1.86 (dq, J=3.4 and 12.6); 3H 0.94 (d, J=7.2 Hz); 6H 0.85 (dd, J=1.2 and 6.6 Hz); 9H 0.90~1.80(m)

[0046] (GC-MS analysis results) GC-MS m / z= 152 (3), 137 (5), 124 (5), 109 (100), 95 (19), 83 (52), 67 (61), 55 (53)

[0047] Example 3 and Comparative Examples 1-2 (Japonica-type fragrance compositions) To the blended fragrance base (daphne type) shown in Table 1, 10 parts by mass of the alicyclic alcohol obtained in Example 2 was added, and an aroma evaluation was carried out. Note that Comparative Example 1 was a blended fragrance in which 10 parts by mass of dipropylene glycol was added instead of the alicyclic alcohol, and Comparative Example 2 was a blended fragrance in which 10 parts by mass of hydroxycitronellal (3,7-dimethyl-7-hydroxyoctanal, having a floral fragrance of lily of the valley) was added instead of the alicyclic alcohol. The aroma evaluation was carried out in the same manner as for the blended fragrance of Example 3, and a comparison was made with the blended fragrance of Example 3.

[0048] [Table 1]

[0049] Compared to the fragrance composition of Comparative Example 1, the fragrance composition of Example 3 had an enhanced jasmine-like floral scent and was imparted with a soft woody scent. Furthermore, the fragrance composition of Example 3 had a broader overall fragrance structure than the fragrance composition of Comparative Example 2. Furthermore, the fragrance composition of Example 3 imparted a softer woody fragrance than the fragrance composition of Comparative Example 2. Furthermore, the fragrance composition of Comparative Example 2 had a more pronounced lily of the valley floral fragrance than the fragrance composition of Comparative Example 1.

[0050] Example 4 and Comparative Examples 3 to 4 (Citrus Woody Fragrance Compositions) To the blended fragrance base (citrus woody) shown in Table 2, 12 parts by mass of the alicyclic alcohol obtained in Example 2 was added, and an odor evaluation was performed. The blended fragrance in which 12 parts by mass of dipropylene glycol was added instead of the alicyclic alcohol was designated Comparative Example 3, and the blended fragrance in which 12 parts by mass of cedrol (octahydro-3,6,8,8-tetramethyl-1H, having a woody cedarwood odor) was added instead of the alicyclic alcohol was designated Comparative Example 4.

[0051] [Table 2]

[0052] Compared to the fragrance composition of Comparative Example 3, the fragrance composition of Example 4 had an enhanced citrus woody fruitiness and an emphasized soft woody scent like sandalwood, and the fragrance had high diffusibility and lingering properties. Furthermore, the fragrance composition of Comparative Example 4 had a more emphasized woody note than the fragrance composition of Comparative Example 3, but the fragrance composition of Example 4 had an even more emphasized soft woody scent like sandalwood than the fragrance composition of Comparative Example 4, the citrus woody juiciness was amplified, and the fragrance had high diffusibility and lingering properties.

[0053] As shown in Example 2, the alicyclic alcohol represented by formula (1) of the present invention has a complex fragrance containing a floral fragrance and a soft woody fragrance in the after-scent, and has excellent after-scent properties, and is therefore useful as a fragrance. It can be seen that the fragrance compositions of Examples 3 and 4 have an enhanced floral and woody scent and are excellent in lingering fragrance and diffusibility compared to the fragrance composition of the Comparative Example. This shows that the alicyclic alcohol represented by formula (1) of the present invention can impart high diffusibility to blended fragrances compared to other substances with floral and woody scents, and can also impart lingering fragrance, making it useful as a raw material for blended fragrances. It can also be seen that fragrance compositions containing the alicyclic alcohol represented by formula (1), which has excellent diffusibility, are useful as fragrance components for various products. Furthermore, as shown in Example 1, the alicyclic alcohol composition of the present invention containing the alicyclic alcohol represented by formula (1) and the alicyclic alcohol represented by formula (2) also has a floral scent of lily of the valley, jasmine, and rose, with a woody scent as a lingering fragrance, and is therefore useful as a fragrance.

Claims

1. Alicyclic alcohols represented by the following formula (1): 【Chemistry 1】

2. A fragrance composition comprising the alicyclic alcohol according to claim 1.

3. An alicyclic alcohol composition containing an alicyclic alcohol represented by the following formula (1) and an alicyclic alcohol represented by the following formula (2): 【Chemistry 2】

4. The alicyclic alcohol composition according to claim 3, further comprising an alicyclic alcohol represented by the following formula (3): 【Transformation 3】

5. The alicyclic alcohol composition according to claim 3 or 4, wherein the total content of the alicyclic alcohol represented by the formula (1) and the alicyclic alcohol represented by the formula (2) is 95 mass% or more.

6. The alicyclic alcohol composition according to any one of claims 3 to 5, wherein the content of the alicyclic alcohol represented by the formula (1) is 85% by mass or more and 98% by mass or less.

7. The alicyclic alcohol composition according to any one of claims 3 to 6, wherein the mass ratio [(1) / (2)] of the alicyclic alcohol represented by formula (1) to the alicyclic alcohol represented by formula (2) in the alicyclic alcohol composition is 85 / 15 to 98 / 2.

8. A fragrance composition comprising the alicyclic alcohol composition according to any one of claims 3 to 7.

9. Alicyclic alcohols represented by the following formula (2): 【Chemistry 4】

10. A fragrance composition comprising the alicyclic alcohol according to claim 9.

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