Cycloaliphatic alcohols, cycloaliphatic alcohol compositions, and perfume compositions

Abstract

Alicyclic alcohol represented by the following formula (1).

Description

Technical Field

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

[0002] Some alicyclic alcohols are known to be used as raw materials for blending fragrances. For example, Non-Patent Literature 1 describes p-isopropylcyclohexylethanol (lily of the valley alcohol) with a floral scent, p-isopropylcyclohexylethanol with a minty, clove, rose, and geranium floral scent, and 2,4-dimethyl-3-cyclohexene-1-methanol with a fresh botanical floral scent reminiscent of hyacinth and lily of the valley as raw materials for blending fragrances, and describes their use in skin care products, etc.

[0003] In addition, Patent Document 1 discloses an alicyclic alcohol compound that has an excellent floral aroma that brings a refreshing and clean feeling.

[0004] Existing technical documents

[0005] Non-patent literature

[0006] Non-patent literature 1: Genichi Into, *Synthetic Fragrance Chemistry and Commercial Knowledge (Revised and Expanded Edition)*, 1996, pp. 54-56, Chemical Industry Daily Press.

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2012-140353 Summary of the Invention

[0009] The problem the invention aims to solve

[0010] As mentioned above, alicyclic alcohols used as fragrances are primarily found in cosmetics, including skincare products, and are also used in various other fields such as perfumes, detergents, groceries, pharmaceuticals, and food. To enhance product value, research and development of new fragrances is ongoing, seeking fragrances with novel scents.

[0011] Therefore, the technical problem to be solved by the present invention is to provide an alicyclic alcohol that has a complex fragrance containing floral notes of lily of the valley, jasmine, and rose, and a lingering fragrance with a soft woody scent. It also has excellent lingering fragrance properties, which can give floral and woody notes diffusion in blended fragrances. It can be used as a fragrance or as a raw material for blended fragrances.

[0012] Solution for solving the problem

[0013] The inventors synthesized and blended various alicyclic alcohols and compositions containing multiple alicyclic alcohols, evaluated their aromas, and found that specific alicyclic alcohols and compositions containing such alicyclic alcohols have excellent fragrance notes, and are therefore excellent as raw materials for blended fragrances, thus completing the present invention.

[0014] That is, the present invention is as follows.

[0015] [1] An alicyclic alcohol, as shown in the following formula (1).

[0016]

[0017] [2] A fragrance composition containing the alicyclic alcohol described in [1] above.

[0018] [3] An alicyclic alcohol composition comprising an alicyclic alcohol as shown in formula (1) and an alicyclic alcohol as shown in formula (2).

[0019]

[0020] [4] The alicyclic alcohol composition according to [3] above further contains an alicyclic alcohol as shown in formula (3) below.

[0021]

[0022] [5] The alicyclic alcohol composition according to [3] or [4] above, wherein the total content of the alicyclic alcohol as shown in formula (1) and the alicyclic alcohol as shown in formula (2) is 95% by mass or more.

[0023] [6] The alicyclic alcohol composition according to any one of [3] to [5] above has an alicyclic alcohol content of 85% by mass or more and 98% by mass or less as shown in formula (1).

[0024] [7] In any one of the above [3] to [6] alicyclic alcohol compositions, the mass ratio of the alicyclic alcohol as shown in formula (1) to the alicyclic alcohol as shown in formula (2) in the alicyclic alcohol composition [(1) / (2)] is 85 / 15 to 98 / 2.

[0025] [8] A fragrance composition comprising any one of the alicyclic alcohol compositions described in any one of [3] to [7].

[0026] [9] An alicyclic alcohol, as shown in the following formula (2).

[0027]

[0028]

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

[0029]

[11] A method for producing an alicyclic alcohol, wherein an aromatic aldehyde as shown in the following general formula (4) is hydrogenated to obtain an alicyclic alcohol as shown in the following general formula (5).

[0030]

[0031] The effects of the invention

[0032] According to the present invention, an alicyclic alcohol is provided which has a complex fragrance containing floral notes of lily of the valley, jasmine, and rose, and a lingering fragrance with a soft woody note, and has excellent lingering fragrance properties, and can therefore be used as a fragrance ingredient. Furthermore, since it can impart diffusion to floral and woody notes in blended fragrances, it can also be used as a raw material for blended fragrances. Detailed Implementation

[0033] [Alicyclic alcohols as shown in formula (1)]

[0034] The alicyclic alcohol of the present invention, as shown in formula (1), is (4-isopropyl-2-methylcyclohexyl)methanol.

[0035]

[0036] The alicyclic alcohols shown in formula (1) have a complex fragrance containing floral notes of lily of the valley, jasmine, and rose, with a lingering woody scent, and excellent lingering aroma, thus they can be used as fragrances. Furthermore, since they can impart diffusion to floral and woody notes in blended fragrances, they can also be used as raw materials for blended fragrances.

[0037] Alicyclic alcohols as shown in formula (1) are preferably obtained by the manufacturing method described later.

[0038] [Alicyclic alcohol composition]

[0039] The alicyclic alcohol composition of the present invention contains an alicyclic alcohol as shown in formula (1) and an alicyclic alcohol as shown in formula (2). The alicyclic alcohol shown in formula (1) is the aforementioned (4-isopropyl-2-methylcyclohexyl)methanol.

[0040]

[0041] <Alicyclic alcohols as shown in formula (2)>

[0042] The alicyclic alcohol contained in the alicyclic alcohol composition of the present invention, as shown in formula (2), is (2-isopropyl-4-methylcyclohexyl)methanol. The alicyclic alcohol shown in formula (2) can also be used as a fragrance.

[0043] <Composition of alicyclic alcohol compositions, etc.>

[0044] The total content of the alicyclic alcohols as shown in formula (1) and the alicyclic alcohols as shown in 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 more preferably 97% by mass or more. There is no upper limit, and it is acceptable to be 100% by mass or less.

[0045] The content of the alicyclic alcohol as shown in 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, more preferably 90% by mass or more, and preferably 98% by mass or less, more preferably 97% by mass or less, and more preferably 95% by mass or less.

[0046] The content of the alicyclic alcohol as shown in 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 preferably 15% by mass or less, more preferably 13% by mass or less, and more preferably 10% by mass or less.

[0047] The mass ratio of the alicyclic alcohol as shown in formula (1) to the alicyclic alcohol as shown in formula (2) in the alicyclic alcohol composition of the present invention [(1) / (2)] is preferably 85 / 15 to 98 / 2, more preferably 87 / 13 to 97 / 3, even more preferably 87 / 13 to 95 / 5, and even more preferably 90 / 10 to 95 / 5.

[0048] The alicyclic alcohol composition of the present invention may also contain an alicyclic alcohol as shown in formula (3) below.

[0049]

[0050] When the alicyclic alcohol composition of the present invention contains an alicyclic alcohol as shown in formula (3), the content of the alicyclic alcohol as shown in formula (3) in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 3% by mass or less, more preferably 2% by mass or less.

[0051] The alicyclic alcohol composition of the present invention having the above composition has a floral fragrance containing lily of the valley, jasmine, and rose, and a woody lingering fragrance, and can be used as a fragrance ingredient. Additionally, it can be used as a raw material for blending fragrances (fragrance compositions) and as an aroma component in various products.

[0052] [Fragrance Composition]

[0053] The fragrance composition of the present invention contains the alicyclic alcohol or the alicyclic alcohol composition.

[0054] That is, the fragrance composition of the first embodiment of the present invention contains an alicyclic alcohol as shown in the following formula (1).

[0055]

[0056] The content of the alicyclic alcohol in the fragrance composition of the present invention can be appropriately adjusted according to the type of fragrance composition, the type of target aroma, and the aroma intensity, and is preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass.

[0057] In addition, the fragrance composition of the second embodiment of the present invention contains an alicyclic alcohol composition, which contains an alicyclic alcohol as shown in formula (1) and an alicyclic alcohol as shown in formula (2).

[0058]

[0059] In the second embodiment of the present invention, the mass ratio of the alicyclic alcohol as shown in formula (1) to the alicyclic alcohol as shown in formula (2) in the fragrance composition is preferably 85 / 15 to 98 / 2, more preferably 87 / 13 to 97 / 3, even more preferably 87 / 13 to 95 / 5, and even more preferably 90 / 10 to 95 / 5.

[0060] Furthermore, the fragrance composition of the second embodiment of the present invention may also contain an alicyclic alcohol as shown in the following formula (3).

[0061]

[0062] The content of the alicyclic alcohol composition in the fragrance composition of the present invention can be appropriately adjusted according to the type of fragrance composition, the type of target aroma, and the aroma intensity, and is preferably 0.01 to 90% by mass, more preferably 0.1 to 50% by mass.

[0063] In the fragrance composition of the present invention, the fragrance component that can be used in combination with the alicyclic alcohol or the alicyclic alcohol composition includes, but is not limited to, the following substances, such as: surfactants such as polyoxyethylene dodecyl 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 valerianene; and linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcene, ethyllinalool, farnesol, nerolidol, cis-3-hexenol, menthol, borneol, β-phenylethanol, benzyl alcohol, benzyl alcohol, and 2,2,6-trimethylcyclohexyl-3- Alcohols such as hexanol, 1-(2-tert-butylcyclohexyloxy)-2-butanol, 4-isopropylcyclohexane-methanol, 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, isoboroylcyclohexanol, and 3,7-dimethyl-7-methoxyoctane-2-ol; phenols such as eugenol, thymol, and vanillin; linaloyl formate, citronellol formate, geraniol formate, n-hexyl acetate, cis-3-hexenyl acetate, linaloyl acetate, citronellol acetate, and acetic acid. Geraniol, Nerolithyl acetate, Terpine acetate, Norbutanyl acetate, Borneol acetate, Isoborneol acetate, o-tert-butylcyclohexyl acetate, p-tert-butylcyclohexyl acetate, Tricyclodecenyl acetate, Benzyl acetate, Styrene acetate, Cinnamyl acetate, Dimethylbenzyl orthoethanol, 3-Pentyltetrahydropyran-4-ylacetate, Citronellol propionate, Tricyclodecenyl propionate, Allyl cyclohexylpropionate, Ethyl 2-cyclohexylpropionate, Benzyl propionate, Citronellol butyrate, Dimethylbenzyl orthoethanol n-butyrate, Tricyclodecenyl isobutyrate, Methyl 2-nonenoate, Methyl benzoate, Benzyl benzoate, Methyl cinnamate, Methyl salicylate, n-hexyl salicylate, Cis-3-hexenyl salicylate, Geraniol, Cis- Esters such as 3-hexenyl ester, methyl jasmonate, dihydrojasmonate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, myricetin, methyl anthranilate, and fruit esters; aldehydes such as n-octanal, n-decanal, n-dodecanoal, 2-methylundecanoal, 10-undecenal, citronellol, citral, dimethyltetrahydrobenzaldehyde, 4(3)-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde, 2-cyclohexylpropanal, p-tert-butyl-α-methylhydrocinnamaldehyde, p-isopropyl-α-methylhydrocinnamaldehyde, p-ethyl-α,α-dimethylhydrocinnamaldehyde, α-pentylcinnamaldehyde, α-hexylcinnamaldehyde, piperaldehyde, and α-methyl-3,4-methylenedioxyhydrocinnamaldehyde;Ketones such as methylheptenone, 4-methylene-3,5,6,6-tetramethyl-2-heptenone, pentylcyclopentanone, 3-methyl-2-(cis-2-penten-1-yl)-2-cyclopenten-1-one, methylcyclopentenone, rose ketone, γ-methylionone, α-ionone, carvone, menthone, camphor, nocaketone, benzylacetone, anisone, methyl β-naphthyl ketone, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, maltol, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, muscone, cycloheptadecone, cyclopentadecanone, cyclohexadecenone, etc.; acetals and ketals of acetaldehyde ethylphenylpropane acetal, citral diethyl acetal, phenylacetaldehyde glycerol acetal, ethyl acetoacetate ethylene glycol ketals, etc. Ethers such as: anisene, β-naphthylmethyl ether, β-naphthylethyl ether, limonene, rose ether, 1,8-cineole, racemic or optically active dodecylhydro-3a,6,6,9a-tetramethylnaphthalene[2,1-b]furan, etc.; nitriles such as citronellol; lactones such as γ-nonanolide, γ-undecanolactone, σ-decanolide, γ-jasmine lactone, coumarin, cyclopentadecanolactone, cyclohexadecylolactone, asterolactone, ethyl brassinate, 11-oxohexadecanolactone, etc.; natural essential oils or natural extracts of orange, lemon, bergamot, citrus, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, geranium, jasmine, ylang-ylang, fennel, clove, ginger, nutmeg, cardamom, cedar, cypress, vetiver, patchouli, rockrose, etc., and other fragrance substances. These other flavoring substances can be blended alone or in combination with other substances.

[0064] In order to impart fragrance and improve the fragrance of the compounding object, the fragrance composition of the present invention can be used as a fragrance component in various products such as perfumes, cosmetics, health and hygiene materials, groceries, beverages, food, pharmaceuticals, and medicines.

[0065] The fragrance composition of the present invention can be used as a fragrance ingredient in products such as perfumes and colognes; hair cosmetics such as shampoos, conditioners, hair growth products, hair creams, hair mousses, hair gels, hair oils, and hair sprays; skin cosmetics such as lotions, serums, creams, lotions, masks, foundations, makeup removers, lipsticks, and other makeup products; hygiene products such as dishwashing liquids, laundry detergents, household cleaners, glass cleaners, fabric softeners, bleach, fragrances, and insecticides; pharmaceuticals such as toothpaste, mouthwash, bath products, antiperspirants, and perming agents; general merchandise such as paper products; pharmaceuticals; and food.

[0066] The content of the fragrance composition of the present invention in the above products can be adjusted appropriately according to the required aroma intensity of each product, preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass.

[0067] Furthermore, the fragrance composition of the third embodiment of the present invention contains an alicyclic alcohol as shown in formula (2). The alicyclic alcohol as shown in formula (2) can also be used as a raw material for blended fragrances (fragrance compositions). The content of the alicyclic alcohol as shown in 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 the substances described above.

[0068] In addition, the content of the flavoring composition in these products is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass.

[0069] [Methods for manufacturing alicyclic alcohols and methods for manufacturing alicyclic alcohol compositions]

[0070] The alicyclic alcohol constituting the alicyclic alcohol composition of the present invention can be obtained by any manufacturing method, but preferably by a manufacturing method that hydrogenates an aromatic aldehyde as shown in general formula (4) to obtain an alicyclic alcohol as shown in general formula (5).

[0071]

[0072] Here, aromatic aldehydes as shown in general formula (4) include aromatic aldehydes as shown in formula (4-1), aromatic aldehydes as shown in formula (4-2), and aromatic aldehydes as shown in formula (4-3).

[0073]

[0074] According to this manufacturing method, an alicyclic alcohol as shown in formula (1) can be obtained from an aromatic aldehyde as shown in formula (4-1), an alicyclic alcohol as shown in formula (2) can be obtained from an aromatic aldehyde as shown in formula (4-2), and an alicyclic alcohol as shown in formula (3) can be obtained from an aromatic aldehyde as shown in formula (4-3).

[0075] The alicyclic alcohol composition of the present invention contains an alicyclic alcohol as shown in formula (1) and an alicyclic alcohol as shown in formula (2). As raw materials, the composition can be obtained directly by hydrogenating a mixture of aromatic aldehydes as shown in formula (4-1) and aromatic aldehydes as shown in formula (4-2), or the composition can be obtained by mixing the individual alicyclic alcohols after obtaining them.

[0076] Alicyclic alcohols represented by the general formula (5) include alicyclic alcohols represented by formula (1), alicyclic alcohols represented by formula (2) and alicyclic alcohols represented by formula (3).

[0077] Aromatic aldehydes, such as those of general formula (4), which are used as raw materials for hydrogenation reactions, can be obtained by any method, but are preferably synthesized by formylation of umbelliferous hydrocarbons (isopropyltoluene) with a superacid, as shown in the following formula.

[0078]

[0079] Formylation of the aromatic aldehyde as shown in formula (4) for use in the manufacturing method of the present invention is preferably a method of reacting cymene with carbon monoxide in the presence of a superacid, and more specifically, a method of reacting cymene with carbon monoxide in the presence of Brønsted acids and Lewis acids such as HF / BF3.

[0080] When HF / BF3 is used as a Brønsted acid and a Lewis acid, the amount of HF is preferably 5 to 25 molar times relative to the umbelliferous hydrocarbons used as raw materials, and the amount of BF3 is preferably 0.2 to 2.5 molar times relative to the umbelliferous hydrocarbons used as raw materials.

[0081] The preferred reaction temperature is -30 to 10℃.

[0082] The reaction is preferably carried out under pressure, with the preferred reaction pressure being 1.0 to 3.0 MPaG.

[0083] The preferred reaction time is 0.2 to 5 hours.

[0084] While aromatic aldehydes as shown in formula (4-1) can be obtained in high yield when using meta-cymenes as raw materials, aromatic aldehydes as shown in formula (4-1) can also be obtained in high yield from p-cymenes by formylation based on the above reaction conditions.

[0085] When p-cymene is formylated, an aromatic aldehyde as shown in formula (4-2) can be obtained as a byproduct. Thus, by using p-cymene as a raw material, a mixture of aromatic aldehydes containing the aromatic aldehydes as shown in formula (4-1) and the aromatic aldehydes as shown in formula (4-2), which are raw materials for the alicyclic alcohol composition of the present invention, can be obtained.

[0086] Compared to metacymenes, paracymenes are available at a lower cost. Therefore, it is preferable to formylate paracymenes or a mixture of paracymenes and metacymenes to obtain an aromatic aldehyde mixture whose main product is an aromatic aldehyde as shown in formula (4-1). The aromatic aldehyde as shown in formula (4-1) is then distilled to obtain an aromatic aldehyde of high purity, which is a raw material for alicyclic alcohols as shown in formula (1).

[0087] Alternatively, it is preferable to obtain an aromatic aldehyde mixture containing aromatic aldehydes as shown in formula (4-1) and aromatic aldehydes as shown in formula (4-2) by formylation of p-cymene or a mixture of p-cymene and meta-cymene, thereby directly using it as a raw material for an alicyclic alcohol composition containing alicyclic alcohols as shown in formula (1) and alicyclic alcohols as shown in formula (2).

[0088] As a method to adjust the ratio of the aromatic aldehyde mixture, the ratio of meta-cymene to para-cymene, used as raw materials, can be adjusted, or the conditions for the formylation reaction of para-cymene can be adjusted. Alternatively, the ratio can be adjusted by distilling the obtained aromatic aldehyde mixture. In this way, an aromatic aldehyde mixture containing aromatic aldehydes as shown in formula (4-1) and aromatic aldehydes as shown in formula (4-2) in any proportion can be obtained. Furthermore, aromatic aldehydes as shown in formula (4-3) are included as byproducts.

[0089] The aromatic aldehydes or mixtures of aromatic aldehydes obtained in this way can be used directly for hydrogenation reactions, or the purity of the target aromatic aldehydes can be improved and adjusted to the target ratio through further purification.

[0090] The reaction conditions for the hydrogenation reaction in the manufacturing method of the present invention are not particularly limited. Preferably, the aromatic aldehyde or mixture of aromatic aldehydes, the hydrogenation catalyst, and the solvent to be added as needed are placed in a pressure vessel and hydrogen is introduced.

[0091] The hydrogenation catalyst used in this reaction can be any conventional metal catalyst used for hydrogenation. Specifically, ruthenium catalyst, palladium catalyst, platinum catalyst, cobalt catalyst, and nickel catalyst can be listed. From the perspective of being able to hydrogenate aromatic rings and aldehyde groups simultaneously, it is preferred to select at least one from the group consisting of ruthenium catalyst, palladium catalyst, and platinum catalyst, and more preferably, a ruthenium catalyst.

[0092] Examples of carriers for metal catalysts include activated carbon, alumina, and diatomaceous earth, with activated carbon being the preferred option.

[0093] In this reaction, a solvent can be used, preferably an alicyclic hydrocarbon compound or a saturated aliphatic hydrocarbon compound, which has no effect on the hydrogenation reaction. It should be noted that it is preferable to practically not use a solvent, as the solvent removal step can be omitted.

[0094] The hydrogen used in this reaction does not require special purification; industrial grade is sufficient. The hydrogen pressure during the reaction is preferably 2.0–20.0 MPa, more preferably 3.0–15.0 MPa, and even more preferably 5.0–10.0 MPa.

[0095] The reaction temperature is preferably 80–150°C, more preferably 110–140°C. Within this range, the hydrogenation decomposition of hydroxyl groups can be suppressed, and the target product can be obtained in high yield, therefore it is preferred.

[0096] The hydrogenation reaction preferably involves the simultaneous hydrogenation of the aromatic ring and the aldehyde group to obtain the target alicyclic alcohol or alicyclic alcohol composition in one step. However, the aromatic ring and the aldehyde group can also be hydrogenated separately, and the reaction can be carried out in two steps.

[0097] The alicyclic alcohols or alicyclic alcohol compositions thus obtained are preferably purified by distillation. The distillation conditions can be adjusted appropriately according to the pressure and temperature during distillation.

[0098] In this way, a cycloaliphatic alcohol composition containing an alicyclic alcohol as shown in formula (1), or an alicyclic alcohol as shown in formula (2), or both an alicyclic alcohol as shown in formula (1) and an alicyclic alcohol as shown in formula (2) can be obtained. These can be used individually as fragrances or mixed in any ratio. Preferably, a cycloaliphatic alcohol composition containing an alicyclic alcohol as shown in formula (1) and an alicyclic alcohol as shown in formula (2) in the above ratio is prepared.

[0099] The alicyclic alcohols obtained as shown in Formula (1) have a complex fragrance containing floral notes of lily of the valley, jasmine, and rose, with a lingering woody aroma. They can be used as fragrances. Furthermore, since they can impart lingering aroma and diffusion to blended fragrances, they can also be used as raw materials for blended fragrances (fragrance compositions). In addition, the alicyclic alcohols shown in Formula (2) can also be used as fragrances. Furthermore, alicyclic alcohol compositions containing both the alicyclic alcohols shown in Formula (1) and Formula (2) have a fragrance containing floral notes of lily of the valley, jasmine, and rose, with a lingering woody aroma. They can be used as fragrances.

[0100] Example

[0101] The present invention will be specifically described based on the embodiments shown below, but the present invention is not limited to these embodiments.

[0102] <Gas Chromatography Analysis (Composition Ratio)>

[0103] The composition ratios of the products obtained in the manufacturing examples and embodiments were determined by gas chromatography based on the following conditions.

[0104] Equipment used: Nexis GC-2030 gas chromatograph (manufactured by Shimadzu Corporation)

[0105] Column: DB-1 (length 30m, inner diameter 0.53mm, film thickness 1.5μm)

[0106] Detector: FID (H2 30mL / min, Air 300mL / min)

[0107] Carrier gas: He (constant flow; average linear velocity 38 cm / s)

[0108] Flow split ratio: 28.1

[0109] Inlet temperature: 300℃

[0110] Detector temperature: 300℃

[0111] Injection volume: 1.0 μL

[0112] Oven temperature: Start at 50℃ and increase to 150℃ at a rate of 5℃ / min. Once at 150℃, increase to 280℃ at a rate of 10℃ / min and hold for 7 minutes. Then increase to 300℃ at a rate of 10℃ / min and hold for 5 minutes.

[0113] <NMR Analysis Methods (Compound Structure)>

[0114] The alicyclic alcohols obtained in Example 2 were analyzed by GC-MS under the following conditions.

[0115] Equipment used: Varian NMR System PS600 600MHz NMR spectrometer

[0116] Resonant frequency: 600MHz

[0117] Measurement temperature: room temperature

[0118] Measurement range: -2≤δ≤14

[0119] Solvent: CDCl3

[0120] Chemical shift reference material: CHCl3 in CDCl3 (δ = 7.26)

[0121] <GC-MS Analysis Methods (Compound Structure)>

[0122] The alicyclic alcohols obtained in Example 2 were analyzed by GC-MS under the following conditions.

[0123] (GC side)

[0124] Equipment used: Gas chromatograph GC2010 Plus (manufactured by Shimadzu Corporation)

[0125] Column: DB-1MS (30m length, 0.25mm inner diameter, 0.25μm film thickness)

[0126] Injection volume: 1 μL

[0127] Vaporization chamber temperature: 300℃

[0128] Carrier gas: He

[0129] Linear velocity control: 38.0 cm / s

[0130] Flow split ratio: 28.1

[0131] Oven temperature: Start at 50℃ and increase to 150℃ at a rate of 5℃ / min. Once at 150℃, increase to 280℃ at a rate of 10℃ / min and hold for 7 minutes. Then increase to 300℃ at a rate of 10℃ / min and hold for 5 minutes.

[0132] (MS side)

[0133] Equipment used: GCMS-QP2010 Ultra (manufactured by Shimadzu Corporation)

[0134] Fragmentation method: EI

[0135] Ion source temperature: 200℃

[0136] Interface temperature: 250℃

[0137] Detector voltage: 0.8kV

[0138] Manufacturing Example 1 (Preparation of a Mixture of Aromatic Aldehydes)

[0139] A 500 mL autoclave equipped with a Nak-driven stirrer and three inlet nozzles at the top and one outlet nozzle at the bottom, with internal temperature control via a sleeve, was used as the formylation reactor. Refrigerant flowed through the sleeve, and 126.5 g (6.32 mol) of hydrogen fluoride was added to the autoclave, which was cooled to -25°C. Then, while stirring and adjusting the temperature to not exceed -25°C, 42.6 g (0.63 mol) of boron trifluoride was added. After adding boron trifluoride, the temperature inside the autoclave was maintained at -25°C, and the pressure was increased to 2 MPaG using carbon monoxide. Then, 56.7 g (0.42 mol) of a m- and p-mixed cymene (isopropyltoluene, m:p (molar ratio) = 68.3:31.7) was added.

[0140] While maintaining a temperature of -25°C and a pressure of 2 MPaG, the reaction mixture in the autoclave was extracted into ice water. After thoroughly mixing the extracted liquid, the oil layer was separated. The oil layer was washed with water to obtain a crude aromatic aldehyde mixture.

[0141] The obtained crude aromatic aldehyde mixture was subjected to a distillation column with 20 theoretical stages to remove low-boiling components. The pressure of the distillation column was set to 15 torr, and the low-boiling components were distilled off until the distillation temperature reached 126°C. The fraction was recovered starting from the point when the distillation temperature reached 126°C, resulting in 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.

[0142] Example 1 (Preparation of alicyclic alcohol composition)

[0143] The aromatic aldehyde mixture obtained in Manufacturing Example 1 was subjected to a hydrogenation reaction.

[0144] 150.0 g of an aromatic aldehyde mixture and 16.5 g (7.5 g dry weight) of a 5% Ru / C catalyst with a water content of 54.7% were added to a 500 mL autoclave. After purging the reactor with nitrogen and hydrogen, hydrogen was introduced to bring the hydrogen pressure to 8.0 MPa. The reaction was carried out at 140 °C with stirring for 6 hours to obtain an alicyclic alcohol composition. The reaction endpoint was the end of hydrogen consumption.

[0145] The resulting alicyclic alcohol composition is 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.

[0146] The resulting alicyclic alcohol composition has a floral aroma containing lily of the valley, jasmine, and rose, with a woody aftertaste.

[0147] Example 2 (Preparation of alicyclic alcohols)

[0148] First, an alicyclic alcohol composition was obtained in the same manner as in Example 1.

[0149] The obtained alicyclic alcohol composition was distilled using a distillation column with a theoretical number of 200 (distillation temperature 121°C, vacuum degree 10 torr) to obtain alicyclic alcohol (4-isopropyl-2-methylcyclohexyl)methanol (formula (1)) with a purity of 98.5% by mass.

[0150] The resulting alicyclic alcohol has a complex aroma with floral notes of lily of the valley, jasmine, and rose, and a lingering woody scent reminiscent of sandalwood.

[0151] The following shows the analytical results of the alicyclic alcohol (4-isopropyl-2-methylcyclohexyl)methanol (formula (1)).

[0152] (NMR analysis results)

[0153] 1¹H NMR (600MHz, CDCl₃) δ²H 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)

[0154] (GC-MS analysis results)

[0155] GC-MS m / z=152(3), 137(5), 124(5), 109(100), 95(19), 83(52), 67(61), 55(53)

[0156] Example 3 and Comparative Examples 1-2 (Daphne-type fragrance compositions)

[0157] Ten parts by weight of the alicyclic alcohol obtained in Example 2 were added to the blended fragrance base (Daphne type) shown in Table 1, and the aroma was evaluated. It should be noted that the blended fragrance with 10 parts by weight of dipropylene glycol added instead of the alicyclic alcohol was used as Comparative Example 1, and the blended fragrance with 10 parts by weight of hydroxycitronellol (3,7-dimethyl-7-hydroxyoctanal, with lily of the valley floral scent) added instead of the alicyclic alcohol was used as Comparative Example 2. The aroma was evaluated in the same way as the blended fragrance of Example 3 and compared with the blended fragrance of Example 3.

[0158] [Table 1]

[0159] Table 1

[0160] Example 3 Comparative Example 1 Comparative Example 2 Blending components (parts by weight) (parts by weight) (parts by weight) Alicyclic alcohols (Example 2) 10 - - Hydroxycitronellal - - 10 dipropylene glycol 5.54 15.54 5.54 Undecyl 0.04 0.04 0.04 benzaldehyde 0.3 0.3 0.3 benzyl acetate 0.7 0.7 0.7 benzyl salicylate 4 4 4 3-(4-Methoxyphenyl)-2-methylpropanal 0.4 0.4 0.4 cis-3-hexenol 0.05 0.05 0.05 3,7-Dimethyl-2,6-Octadialdehyde 0.3 0.3 0.3 Citronellol 0.3 0.3 0.3 Citronellol 4 4 4 Ethylene brassinolate 24 24 24 Hydrogenated methyl rosinate 5 5 5 Methyl dihydrojasmonic acid 12 12 12 Piperylpropionaldehyde 0.5 0.5 0.5 Indole 0.04 0.04 0.04 α-Indole 1.2 1.2 1.2 Linalool 10 10 10 Methyl anthranilate 0.03 0.03 0.03 γ-methylionone 0.7 0.7 0.7 Neroli 2.5 2.5 2.5 Sweet orange terpenes 6 6 6 β-Naphthyl ketone 0.4 0.4 0.4 2-Phenylenol 4.5 4.5 4.5 Roman Musk 5 5 5 Isoborneol 2.5 2.5 2.5 sum 100 100 100

[0161] Compared with the fragrance composition of Comparative Example 1, the fragrance composition of Example 3 has an enhanced jasmine-like floral fragrance while having a soft woody scent.

[0162] Furthermore, the fragrance composition of Example 3 has a richer overall aroma framework compared to the fragrance composition of Comparative Example 2. Additionally, the fragrance composition of Example 3 is endowed with a softer woody aroma compared to the fragrance composition of Comparative Example 2. It should be noted that the fragrance composition of Comparative Example 2 has a stronger lily-of-the-valley floral scent compared to the fragrance composition of Comparative Example 1.

[0163] Example 4 and Comparative Examples 3-4 (Fragrance Compositions of Citrus Wood)

[0164] Aroma was evaluated by adding 12 parts by weight of the alicyclic alcohol obtained in Example 2 to the blended flavor base (citrus wood) shown in Table 2. It should be noted that a blended flavor with 12 parts by weight of dipropylene glycol added instead of the alicyclic alcohol was used as Comparative Example 3, and a blended flavor with 12 parts by weight of cedrol (octahydro-3,6,8,8-tetramethyl-1H, possessing the woody aroma of cedar) added instead of the alicyclic alcohol was used as Comparative Example 4.

[0165] [Table 2]

[0166] Table 2

[0167] Example 4 Comparative Example 3 Comparative Example 4 Blending components (parts by weight) (parts by weight) (parts by weight) Alicyclic alcohols (Example 2) 12 - - Cedarwood - - 12 dipropylene glycol 24.04 36.04 24.04 Camphor 0.03 0.03 0.03 Virginia Cedar 1.2 1.2 1.2 cis-3-hexenol 1.2 1.2 1.2 Citral dimethyl acetal 0.2 0.2 0.2 γ-decanolide 0.8 0.8 0.8 methyl o-aminobenzoate 0.03 0.03 0.03 Olive resin 1.4 1.4 1.4 ethyl 2-methylbutyrate 0.06 0.06 0.06 Oxacyclohexadecane-2-one 0.1 0.1 0.1 γ-terpinene 2 2 2 Geraniol 2.5 2.5 2.5 Geraniol acetate 0.3 0.3 0.3 grapefruit oil 13 13 13 Lemon oil 10 10 10 White lemon oil terpenes 8 8 8 Linalool 20 20 20 Linaloyl acetate 0.3 0.3 0.3 β-pinene 2.5 2.5 2.5 Marigold oil 0.04 0.04 0.04 α-Terpineol 0.3 0.3 0.3 sum 100 100 100

[0168] Compared with the fragrance composition of Comparative Example 3, the fragrance composition of Example 4 has an increased citrus-woody juiciness, a stronger sandalwood-like soft woody aroma, and higher diffusion and lingering fragrance.

[0169] In addition, compared with the fragrance composition of Comparative Example 3, the fragrance composition of Comparative Example 4 has a stronger woody aroma, while the fragrance composition of Example 4 has a further enhanced sandalwood-like soft woody aroma, an increased citrus-woody juiciness, and higher fragrance diffusion and lingering.

[0170] As shown in Example 2, it can be seen that the alicyclic alcohol of the present invention, represented by Formula (1), has a complex fragrance with floral and lingering aromas and a soft woody scent, and has excellent lingering aroma properties, and therefore can be used as a fragrance.

[0171] Compared with the fragrance compositions of the comparative examples, the fragrance compositions of Examples 3 and 4 show enhanced floral and woody notes, and excellent residual aroma and diffusivity. Therefore, it is evident that the alicyclic alcohols of the present invention, as shown in Formula (1), can impart high diffusivity and residual aroma to blended fragrances compared to other substances with floral and woody notes, and thus can also be used as raw materials for blended fragrances. Furthermore, it is known that fragrance compositions containing alicyclic alcohols of Formula (1) with excellent diffusivity can also be used as flavoring ingredients in various products.

[0172] Furthermore, as shown in Example 1, it can be seen that the alicyclic alcohol composition of the present invention containing alicyclic alcohols as shown in Formula (1) and alicyclic alcohols as shown in Formula (2) also has the floral fragrance of lily of the valley, jasmine, and rose, and the residual fragrance with a woody aroma, and can be used as a fragrance.

Claims

1. A cycloaliphatic alcohol composition comprising a cycloaliphatic alcohol represented by the following formula (1) and a cycloaliphatic alcohol represented by the following formula (2), wherein, The mass ratio [(1) / (2)] of the alicyclic alcohol as shown in the formula (1) and the alicyclic alcohol as shown in the formula (2) in the alicyclic alcohol composition is 85 / 15 to 98 / 2, 2. The alicyclic alcohol composition according to claim 1, further containing an alicyclic alcohol as shown in the following formula (3), 3. The cycloaliphatic alcohol composition of claim 1 or 2, wherein, The total content of the alicyclic alcohol as shown in the formula (1) and the alicyclic alcohol as shown in the formula (2) is 95 mass% or more.

4. The cycloaliphatic alcohol composition of claim 1 or 2, wherein, The content of the alicyclic alcohol as shown in the formula (1) is 85 mass% or more and 98 mass% or less.

5. A perfume composition containing the alicyclic alcohol composition according to any one of claims 1 to 4.

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