Cycloaliphatic alcohols, cycloaliphatic alcohol compositions, and perfume compositions

Abstract

Alicyclic alcohol represented by the following general 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 (Mayol) as having a floral scent; p-isopropylcyclohexylethanol as having a peppermint-like scent of clove, rose, and geranium; and 2,4-dimethyl-3-cyclohexene-1-methanol as having a fresh, green, and floral scent reminiscent of hyacinth and lily of the valley. Non-Patent Literature 1 describes various alicyclic alcohols, including these, as raw materials for blending fragrances, and their uses include skincare products.

[0003] In addition, Patent Document 1 discloses a 4-isobutylcyclohexyl methanol and fragrance composition having a floral fragrance, a rose fragrance, a citronellol fragrance, a light lily of the valley fragrance, and an osmanthus fragrance.

[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. 1-207252 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 floral and fruity aroma. In blended fragrances, it can enhance the moistness, floral aroma, and fruity aroma on the basis of the aforementioned aroma. It can be used as a fragrance ingredient or as a raw material for blended fragrances. Furthermore, the technical problem to be solved by the present invention also includes providing a method for manufacturing the alicyclic alcohol, an alicyclic alcohol composition containing the alicyclic alcohol, and a fragrance composition.

[0012] Solution for solving the problem

[0013] The inventors synthesized and blended various alicyclic alcohols and compositions containing multiple of these alicyclic alcohols, and evaluated their aromas. They found that specific alicyclic alcohols and compositions containing these 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, which is shown in the following general formula (1),

[0016]

[0017] [2] According to the alicyclic alcohol described in [1] above, it is represented by the following general formula (2).

[0018]

[0019] In the formula, R can be chosen arbitrarily. 1 It is methyl and R 2 It is isobutyl or R 1 It is isobutyl and R 2 It is a methyl group.

[0020] [3] The alicyclic alcohols according to [1] or [2] above are as shown in the following formula (3).

[0021]

[0022] [4] The alicyclic alcohols according to [1] or [2] above are as shown in the following formula (4).

[0023]

[0024] [5] An alicyclic alcohol composition comprising an alicyclic alcohol of formula (3) and an alicyclic alcohol of formula (4).

[0025]

[0026] [6] According to the alicyclic alcohol composition described in [5] above, the ratio of the alicyclic alcohol represented by formula (3) to the alicyclic alcohol represented by formula (4) [(3) / (4)] is 7 / 93 to 98 / 2 in terms of peak area ratio in gas chromatography.

[0027] [7] A fragrance composition comprising any one of the alicyclic alcohols described in [1] to [4] above or the alicyclic alcohol composition described in [5] or [6] above.

[0028] [8] A method for producing an alicyclic alcohol, wherein an aromatic aldehyde of general formula (5) is hydrogenated to obtain an alicyclic alcohol of general formula (6).

[0029]

[0030] [9] According to the method for manufacturing alicyclic alcohols described in [8] above, an aromatic aldehyde of the following general formula (7) is hydrogenated to obtain an alicyclic alcohol of the following general formula (1).

[0031]

[0032] The effects of the invention

[0033] According to the present invention, an alicyclic alcohol can be provided, which, due to its floral and fruity aroma, can be used as a fragrance; furthermore, since it can enhance the moistness, floral aroma, and fruity aroma in blended fragrances, it can also be used as a raw material for blended fragrances. Furthermore, a method for manufacturing the alicyclic alcohol, an alicyclic alcohol composition containing the alicyclic alcohol, and a fragrance composition can also be provided. Attached Figure Description

[0034] Figure 1-1 This is an example of the NMR analysis results of the alicyclic alcohol (4-isobutyl-2-methylcyclohexyl)methanol (formula (3)) of the present invention.

[0035] Figure 1-2 yes Figure 1-1 A magnified view of the NMR analysis results shown.

[0036] Figure 1-3 yes Figure 1-1 A magnified view of the NMR analysis results shown.

[0037] Figure 1-4 yes Figure 1-1 A magnified view of the NMR analysis results shown.

[0038] Figure 1-5 yes Figure 1-1 A magnified view of the NMR analysis results shown.

[0039] Figure 2 This is an example of the GC-MS analysis results of the alicyclic alcohol (4-isobutyl-2-methylcyclohexyl)methanol (formula (3)) of the present invention.

[0040] Figure 3-1 This is an example of the NMR analysis results of the alicyclic alcohol (2-isobutyl-4-methylcyclohexyl)methanol (formula (4)) of the present invention.

[0041] Figure 3-2 yes Figure 3-1 A magnified view of the NMR analysis results shown.

[0042] Figure 3-3 yes Figure 3-1 A magnified view of the NMR analysis results shown.

[0043] Figure 3-4 yes Figure 3-1 A magnified view of the NMR analysis results shown.

[0044] Figure 3-5 yes Figure 3-1 A magnified view of the NMR analysis results shown.

[0045] Figure 4 This is an example of the GC-MS analysis results of the alicyclic alcohol (2-isobutyl-4-methylcyclohexyl)methanol (formula (4)) of the present invention. Detailed Implementation

[0046] [Alicyclic alcohols]

[0047] The alicyclic alcohols of the present invention are shown in the following general formula (1).

[0048]

[0049] Alicyclic alcohols represented by general formula (1) can be used as fragrances because they have floral and fruity aromas. In addition, they can also be used as raw materials for blending fragrances because they can enhance the moist, floral, and fruity aromas on top of the aforementioned fragrances.

[0050] The alicyclic alcohols represented by general formula (1) are preferably obtained by the manufacturing method described later.

[0051] Among the alicyclic alcohols represented by general formula (1), the alicyclic alcohols represented by general formula (2) below are preferred.

[0052]

[0053] In the formula, R can be chosen arbitrarily. 1 It is methyl and R 2 It is isobutyl or R 1 It is isobutyl and R 2 It is a methyl group.

[0054] The alicyclic alcohol represented by general formula (1) is more preferably an alicyclic alcohol represented by formula (3) or formula (4) below. Additionally, the alicyclic alcohol represented by general formula (2) is an alicyclic alcohol represented by formula (3) or formula (4) below.

[0055]

[0056] The alicyclic alcohols shown in formula (3) have floral and fruity aromas, and therefore can be used as fragrances. In addition, since they can enhance the moist, floral, and fruity aromas on top of the aforementioned fragrances, they can also be used as raw materials for blending fragrances.

[0057] In addition, the alicyclic alcohols shown in formula (4) also have floral and fruity aromas, and therefore can also be used as fragrances. Furthermore, since they can enhance the moist, floral, and fruity aromas on top of the aforementioned fragrances, they can also be used as raw materials for blending fragrances.

[0058] The alicyclic alcohols shown in formula (3) and formula (4) are preferably obtained by the manufacturing methods described later.

[0059] [Alicyclic alcohol composition]

[0060] Compositions containing two or more alicyclic alcohols of the general formula (1) also exhibit the above-mentioned effects and are therefore preferred.

[0061] More preferably, it is an alicyclic alcohol composition containing an alicyclic alcohol of formula (3) and an alicyclic alcohol of formula (4).

[0062]

[0063] <Composition of alicyclic alcohol compositions, etc.>

[0064] Based on the peak area ratio in gas chromatography, the total content of the alicyclic alcohols as shown in formula (3) and formula (4) in the alicyclic alcohol composition of the present invention is preferably 95% or more, more preferably 96% or more, and more preferably 97% or more. There is no upper limit; 100% or less is acceptable.

[0065] Based on the peak area ratio in gas chromatography, the content of the alicyclic alcohol as shown in formula (3) in the alicyclic alcohol composition of the present invention is preferably 2% or more, more preferably 5% or more, more preferably 7% or more, even more preferably 70% or more, even more preferably 80% or more, even more preferably 85% or more. Furthermore, it is preferably 98% or less, more preferably 95% or less, even more preferably 90% or less.

[0066] Based on the peak area ratio in gas chromatography, the content of the alicyclic alcohol as shown in formula (4) in the alicyclic alcohol composition of the present invention is preferably 2% or more, more preferably 5% or more, and more preferably 10% or more. Furthermore, it is preferably 98% or less, more preferably 95% or less, more preferably 93% or less, even more preferably 30% or less, even more preferably 20% or less, and even more preferably 15% or less.

[0067] Based on the peak area ratio in gas chromatography, the ratio of the alicyclic alcohol as shown in formula (3) to the alicyclic alcohol as shown in formula (4) in the alicyclic alcohol composition of the present invention [(3) / (4)] is preferably 2 / 98 to 98 / 2, more preferably 5 / 95 to 98 / 2, more preferably 7 / 93 to 98 / 2, even more preferably 10 / 90 to 98 / 2, even more preferably 70 / 30 to 98 / 2, even more preferably 80 / 20 to 95 / 5, even more preferably 85 / 15 to 90 / 10.

[0068] It should be noted that the peak area ratio and peak area proportion in the gas chromatography can be determined by the chromatogram obtained by gas chromatography.

[0069] Specifically, a nonpolar chromatographic column is used, and an FID detector is used. The result is obtained by gas chromatography with a temperature of 150°C to 300°C.

[0070] More specifically, it is determined by chromatography performed using the methods described in the examples.

[0071] The alicyclic alcohol composition of the present invention having the above composition can be used as a fragrance because it has a floral and fruity aroma. Furthermore, it can also be used as a raw material for blended fragrances because it can enhance the moisturizing, floral, and fruity aromas on top of the aforementioned fragrance, and can be used as an aroma component in various products.

[0072] [Fragrance Composition]

[0073] The fragrance composition of the present invention contains the alicyclic alcohol or the alicyclic alcohol composition.

[0074] That is, the fragrance composition of the first embodiment of the present invention contains an alicyclic alcohol represented by the following general formula (1).

[0075] The fragrance composition of the first embodiment of the present invention contains the alicyclic alcohol having floral and fruity aromas, thus enhancing the moisturizing, floral, and fruity aromas in blended fragrances (fragrance compositions).

[0076]

[0077] The alicyclic alcohol contained in the fragrance composition of the first embodiment of the present invention is an alicyclic alcohol represented by the general formula (1), preferably an alicyclic alcohol represented by the general formula (2), and more preferably an alicyclic alcohol represented by the formula (3).

[0078] 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.

[0079] In addition, the fragrance composition of the second embodiment of the present invention comprises an alicyclic alcohol composition containing two or more of the alicyclic alcohols represented by the general formula (1).

[0080] The alicyclic alcohol composition contained in the fragrance composition of the second embodiment of the present invention is preferably an alicyclic alcohol composition containing an alicyclic alcohol represented by formula (3) or an alicyclic alcohol represented by formula (4) below, and more preferably an alicyclic alcohol composition containing an alicyclic alcohol represented by formula (3) below and an alicyclic alcohol represented by formula (4) below.

[0081] The fragrance composition of the second embodiment of the present invention contains the alicyclic alcohol composition having floral and fruity aromas, thus enhancing the moisturizing, floral, and fruity aromas on the basis of the aroma in blended fragrances (fragrance compositions).

[0082]

[0083] 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.

[0084] In the following description, "fragrance composition of the present invention" refers to both "fragrance composition of the first embodiment of the present invention" and "fragrance composition of the second embodiment of the present invention".

[0085] In the fragrance composition of the present invention, there are no limitations on the components that can be used in combination with the alicyclic alcohol or the alicyclic alcohol composition, and the following components can be cited as examples.

[0086] For example, surfactants, solvents, and other flavoring substances other than the alicyclic alcohols represented by the general formula (1) can be listed.

[0087] In particular, by combining it with other fragrance substances other than the alicyclic alcohols shown in the general formula (1), the fragrance composition can be endowed with floral and fruity aromas, which can enhance the moist, floral, and fruity feel. Therefore, the fragrance composition of the present invention preferably contains other fragrance substances other than the alicyclic alcohols shown in the general formula (1).

[0088] Examples of surfactants include polyoxyethylene lauryl sulfate.

[0089] Examples of solvents include dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, triethyl citrate, and ethanol.

[0090] In addition, other fragrance substances other than the alicyclic alcohols represented by the general formula (1) that can be used in the fragrance compositions of the present invention are preferably selected from at least one of the group consisting of hydrocarbons, alcohols, phenols, esters, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, natural essential oils and natural extracts.

[0091] Specific examples of flavoring substances other than the alicyclic alcohols represented by the general formula (1) include, for example: hydrocarbons such as limonene, α-pinene, β-pinene, terpinene, cedrene, longleafene, and valencene; linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcene, ethyllinalool, farnesol, nerolidol, cis-3-hexenol, menthol, borneol, β-phenylethanol, benzyl alcohol, benzyl alcohol, 2,2,6-trimethylcyclohexyl-3-hexanol, 1-(2-tert-butylcyclohexyloxy)-2-butanol, 4-isopropylcyclohexaneethanol, 4-methyl-2-(2-methylpropyl) Alcohols such as 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, isoborneol, 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, geraniol acetate, nerol acetate, terpineol acetate, norberyl acetate, borneol acetate, and isoborneol acetate. Esters, o-tert-butylcyclohexyl acetate, p-tert-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styrene acetate, cinnamic acid ester, dimethyl benzyl orthoethanol, 3-pentyltetrahydropyran-4-ylacetate, citronellol propionate, tricyclodecenyl propionate, allyl cyclohexylpropionate, ethyl 2-cyclohexylpropionate, benzyl propionate, citronellol butyrate, dimethyl benzyl orthoethanol butyrate, tricyclodecenyl isobutyrate, methyl nonenoate, methyl benzoate, benzyl benzoate, methyl cinnamate, methyl salicylate, n-hexyl salicylate, cis-3-hexenyl salicylate, geraniol, cis-3-hexenyl salicylate, methyl jasmonate, dihydrojasmonate Esters such as methyl benzoate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, myricetin, methyl anthranilate, and fruit flavor 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;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-methyl ionone, α-ionone, carvone, menthone, camphor, nocaketone, benzylacetone, anisylacetone, methyl β-naphthyl ketone, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, maltol, 7-ethyl Acyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, muscone, civetone, cyclopentadecanone, cyclohexadecenone, and other ketones; acetals and ketals of acetaldehyde ethylphenylpropane acetal, citral diethyl acetal, phenylacetaldehyde glycerol acetal, ethyl acetoacetate, and ethylene glycol ketals; anethole, β-naphthylmethyl ether, β-naphthylethyl ether, limonene oxide, and rose ether. Ethers such as oxide, 1,8-cineole, racemic or optically active dodecyl-3a,6,6,9a-tetramethylnaphthalene[2,1-b]furan; nitriles such as citronellol; lactones such as γ-nonanolide, γ-undecanolactone, σ-decanolide, γ-jasmine lactone, coumarin, cyclopentadecanolactone, cyclohexadecylolactone, asterolactone, ethylene brassylate, 11-oxahexadecylolactone, etc.; natural essential oils or extracts of orange, lemon, bergamot, citrus, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, geranium, jasmine, ylang-ylang, fennel, clove, ginger, nutmeg, cardamom, cedarwood, cypress, vetiver, patchouli, rockrose, etc. These fragrance substances can be blended alone or in combination.

[0092] In order to impart fragrance and improve the fragrance of the compounding target, 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, quasi-pharmaceuticals, and pharmaceuticals.

[0093] 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.

[0094] 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.

[0095] [Methods for manufacturing alicyclic alcohols and methods for manufacturing alicyclic alcohol compositions]

[0096] The alicyclic alcohols of the present invention and the alicyclic alcohols constituting the alicyclic alcohol compositions of the present invention can be obtained by any manufacturing method.

[0097] The preferred method for producing the alicyclic alcohol of the present invention is to hydrogenate an aromatic aldehyde of the following general formula (5) to obtain the alicyclic alcohol of the following general formula (6).

[0098]

[0099] The aromatic aldehyde represented by general formula (5) is preferably an aromatic aldehyde represented by general formula (7) below. Therefore, a more preferred method for producing the alicyclic alcohol of the present invention is a method of hydrogenating the aromatic aldehyde represented by general formula (7) below to obtain the alicyclic alcohol represented by general formula (1) below.

[0100]

[0101] The aromatic aldehydes represented by general formula (7) include aromatic aldehydes represented by general formula (7-1) below. Furthermore, the aromatic aldehydes represented by formula (7-1) below are aromatic aldehydes represented by formula (7-2) below or aromatic aldehydes represented by formula (7-3) below.

[0102]

[0103] In the formula, R can be chosen arbitrarily. 1 It is methyl and R 2 It is isobutyl or R 1 It is isobutyl and R 2 It is a methyl group.

[0104] According to this manufacturing method, an alicyclic alcohol of general formula (2) can be obtained from an aromatic aldehyde of general formula (7-1). Specifically, an alicyclic alcohol of formula (3) can be obtained from an aromatic aldehyde of formula (7-2), and an alicyclic alcohol of formula (4) can be obtained from an aromatic aldehyde of formula (7-3).

[0105] As for the alicyclic alcohol composition containing the alicyclic alcohols of formula (3) and formula (4) of the present invention, the composition can be obtained directly by hydrogenating the mixture of aromatic aldehydes of formula (7-2) and formula (7-3) as raw materials; or the composition can be obtained by mixing the alicyclic alcohols after obtaining each alicyclic alcohol.

[0106] Aromatic aldehydes of general formula (5) that are used as raw materials for hydrogenation reactions can be obtained by any method, but are preferably synthesized by formylation of isobutyltoluene with a superacid as shown in the following formula.

[0107]

[0108] To obtain the aromatic aldehyde represented by formula (5) that can be used in the manufacturing method of the present invention, the formylation is preferably carried out by reacting isobutyltoluene with carbon monoxide in the presence of a superacid, and more specifically, by reacting isobutyltoluene with carbon monoxide in the presence of Brønsted acids and Lewis acids such as HF / BF3.

[0109] When HF / BF3 is used as Brønsted acid and Lewis acid, the amount of HF used is preferably 5 to 25 moles more than that of isobutyltoluene used as a raw material, and the amount of BF3 used is preferably 0.2 to 2.5 moles more than that of isobutyltoluene used as a raw material.

[0110] The preferred reaction temperature is -30 to 10℃.

[0111] The reaction is preferably carried out under pressure, with the preferred reaction pressure being 1.0 to 3.0 MPaG.

[0112] The preferred reaction time is 0.2 to 5 hours.

[0113] As a method to adjust the proportion of the aromatic aldehyde mixture, the conditions of the formylation reaction can be adjusted. The proportion can be adjusted by distilling the obtained aromatic aldehyde mixture. In this way, an aromatic aldehyde mixture containing the aromatic aldehydes shown in formula (7-2) and formula (7-3) in any proportion can be obtained.

[0114] The aromatic aldehydes or mixtures of aromatic aldehydes obtained in this way can be used directly for hydrogenation reactions, and the purity of the target aromatic aldehyde can be improved through further purification. Alternatively, they can be separated by distillation or mixed with other aromatic aldehydes or mixtures of aromatic aldehydes to adjust to the target ratio.

[0115] The reaction conditions for the hydrogenation reaction in the manufacturing method of the present invention are not particularly limited. Preferably, the aromatic aldehyde or a mixture of aromatic aldehydes, a hydrogenation catalyst, a solvent to be added as needed, etc., are placed in a pressure vessel and hydrogen is introduced.

[0116] 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 of the group consisting of ruthenium catalyst, palladium catalyst, and platinum catalyst, and more preferably, ruthenium catalyst.

[0117] Examples of carriers for metal catalysts include activated carbon, alumina, and diatomaceous earth, with activated carbon being the preferred option.

[0118] In this reaction, a solvent can be used, preferably a solvent that has no effect on the hydrogenation reaction of alicyclic hydrocarbons and saturated aliphatic hydrocarbons. It should be noted that since a solvent removal step is not required, it is preferable to use virtually no solvent.

[0119] The hydrogen used in this reaction does not need to be specially purified; 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.

[0120] The reaction temperature is preferably 80–150°C, more preferably 110–140°C. Within this range, side reactions can be suppressed, and the target product can be obtained in high yield, therefore it is preferred.

[0121] The hydrogenation reaction is preferably carried out by hydrogenating both the aromatic ring and the aldehyde group simultaneously to obtain the target alicyclic alcohol or alicyclic alcohol composition in one step. However, the reaction can also be carried out in two stages to hydrogenate the aromatic ring and the aldehyde group separately.

[0122] The resulting alicyclic alcohols or alicyclic alcohol compositions are preferably purified by distillation. The distillation conditions can be adjusted appropriately according to the pressure and temperature during distillation.

[0123] In this way, alicyclic alcohols represented by general formula (1), general formula (2), formula (3), and formula (4) can be obtained respectively. Furthermore, alicyclic alcohol compositions containing two or more alicyclic alcohols of general formula (1), and alicyclic alcohol compositions containing both alicyclic alcohols of formula (3) and formula (4) can be obtained. These can be used individually as flavorings or mixed in any proportion. Preferably, the alicyclic alcohol composition contains alicyclic alcohols of formula (3) and formula (4) in the above proportions.

[0124] The alicyclic alcohols represented by the general formula (1) can be used as fragrances because they have floral and fruity aromas. Furthermore, they can also be used as raw materials for blended fragrances (fragrance compositions) because they can enhance the moist, floral, and fruity aromas on the basis of the aromas.

[0125] Example

[0126] The present invention will be specifically described based on the embodiments shown below, but the present invention is not limited to these embodiments.

[0127] <Component ratios of alicyclic alcohols and compositional ratios of alicyclic alcohol compositions>

[0128] The component ratios and composition ratios of the products obtained in the examples can be calculated based on the peak areas in the chromatograms obtained by gas chromatography under the following conditions, using the following formula. It should be noted that the proportions of each alicyclic alcohol in the alicyclic alcohol composition are obtained by the following formula, and then the composition ratio of the alicyclic alcohol composition ((3) / (4) ratio) is calculated from these proportions.

[0129] The percentage of alicyclic alcohols (%) = Peak area of ​​the target alicyclic alcohol / Sum of the areas of all peaks excluding solvents × 100

[0130] The percentage (%) of the target alicyclic alcohol (the alicyclic alcohol shown in formula (3) or the alicyclic alcohol shown in formula (4)) in the alicyclic alcohol composition = peak area of ​​the target alicyclic alcohol / sum of peak areas of the alicyclic alcohol shown in formula (3) and the alicyclic alcohol shown in formula (4) × 100

[0131] (Gas Chromatography Analysis)

[0132] Equipment used: Nexis GC-2030 gas chromatograph (manufactured by Shimadzu Corporation)

[0133] Column: DB-1 (non-polar, 100% polydimethylsiloxane, 30m in length, 0.53mm in inner diameter, 1.5μm in film thickness)

[0134] Detector: FID (H2 30mL / min, Air 300mL / min)

[0135] Carrier gas: He (constant flow; average linear velocity 38 cm / s)

[0136] Flow split ratio: 28.1

[0137] Inlet temperature: 300℃

[0138] Detector temperature: 300℃

[0139] Injection volume: 1.0 μL

[0140] Oven temperature: Start at 50℃ and increase to 150℃ at a rate of 5℃ / minute. After reaching 150℃, increase to 280℃ at a rate of 10℃ / minute and hold for 7 minutes. Then increase to 300℃ at a rate of 10℃ / minute and hold for 5 minutes.

[0141] <Structure of Compounds>

[0142] The alicyclic alcohols and compositions obtained in the examples were subjected to NMR and GC-MS (gas chromatography-mass spectrometry) analysis under the following conditions.

[0143] (NMR analysis method)

[0144] Equipment used: Varian NMR System PS600 600MHz NMR spectrometer

[0145] Resonant frequency: 600MHz

[0146] Measurement temperature: room temperature

[0147] Measurement range: -2≤δ≤14

[0148] Solvent: CDCl3

[0149] Chemical shift reference material: CHCl3 in CDCl3 (δ = 7.26)

[0150] (GC-MS analysis method)

[0151] (GC side)

[0152] Equipment used: Gas chromatograph GC2010 Plus (manufactured by Shimadzu Corporation)

[0153] Column: DB-1MS (30m length, 0.25mm inner diameter, 0.25μm film thickness)

[0154] Injection volume: 1 μL

[0155] Vaporization chamber temperature: 300℃

[0156] Carrier gas: He

[0157] Linear velocity control: 38.0 cm / s

[0158] Flow split ratio: 28.1

[0159] Oven temperature: Start at 50℃ and increase to 150℃ at a rate of 5℃ / minute. After reaching 150℃, increase to 280℃ at a rate of 10℃ / minute and hold for 7 minutes. Then increase to 300℃ at a rate of 10℃ / minute and hold for 5 minutes.

[0160] (MS side)

[0161] Equipment used: GCMS-QP2010 Ultra (manufactured by Shimadzu Corporation)

[0162] Fracturing methods: EI (Example 2), CI (Example 3)

[0163] Ion source temperature: 200℃

[0164] Interface temperature: 250℃

[0165] Detector voltage: 0.8kV

[0166] Manufacturing Example 1 (Preparation of a Mixture of Aromatic Aldehydes)

[0167] As a formylation reactor, a 500 mL autoclave equipped with a magnetically driven stirrer, three inlet nozzles at the top, one outlet nozzle at the bottom, and internal temperature control via a jacket was used. Refrigerant was introduced through the jacket, and 104.6 g (5.23 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, 79.9 g (1.18 mol) of boron trifluoride was added. After adding boron trifluoride, while maintaining the autoclave temperature at -25°C, the pressure was increased to 2 MPaG using carbon monoxide, and 97.8 g (0.66 mol) of m-isobutyltoluene was added.

[0168] After stirring for 240 minutes at -25°C and 2 MPaG, the reaction mixture in the autoclave was diverted to ice water. The diverted mixture was thoroughly agitated and then separated into an oil layer. The resulting oil layer was washed with water to obtain a mixture of aromatic aldehydes.

[0169] Example 1 (Preparation of alicyclic alcohol composition)

[0170] The aromatic aldehyde mixture obtained in Manufacturing Example 1 was subjected to a hydrogenation reaction.

[0171] 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 (the time when the temperature started to rise was taken as the start of the reaction) to obtain an alicyclic alcohol composition. The endpoint of the reaction was the end of hydrogen consumption.

[0172] The obtained alicyclic alcohol composition was distilled using a distillation column with 80 theoretical stages (residue temperature 132°C, vacuum 10 torr) to obtain the alicyclic alcohol composition.

[0173] The obtained alicyclic alcohol composition contained (4-isobutyl-2-methylcyclohexyl)methanol (Formula (3)) and (2-isobutyl-4-methylcyclohexyl)methanol (Formula (4)) in a ratio of 89.1:10.9 based on the peak area ratio in gas chromatography. Furthermore, the purity of the sum of (4-isobutyl-2-methylcyclohexyl)methanol (Formula (3)) and (2-isobutyl-4-methylcyclohexyl)methanol (Formula (4)) was 99.9% based on the peak area in gas chromatography.

[0174] The resulting alicyclic alcohol composition has a floral and fruity aroma.

[0175] Example 2 (Preparation of alicyclic alcohol ((4-isobutyl-2-methylcyclohexyl)methanol (Formula (3))))

[0176] The aromatic aldehyde mixture obtained in Manufacturing Example 1 was repeatedly distilled using a distillation column with 80 theoretical stages (distillation temperature 150°C, vacuum 9 torr) to obtain 4-isobutyl-2-methylbenzaldehyde. The purity of the obtained 4-isobutyl-2-methylbenzaldehyde, based on the peak area in gas chromatography, was 98.6%. It also contained 0.7% 2-isobutyl-4-methylbenzaldehyde and 0.7% other compounds.

[0177] Using the obtained 2-isobutyl-4-methylbenzaldehyde, the same operation as in Example 1 was performed to obtain (4-isobutyl-2-methylcyclohexyl)methanol (Formula (3)).

[0178] The purity of the obtained (4-isobutyl-2-methylcyclohexyl)methanol (Formula (3)) was 98.6% based on the peak area in gas chromatography.

[0179] Figures 1-1 to 1-5 The NMR analysis results of the alicyclic alcohol (4-isobutyl-2-methylcyclohexyl)methanol (formula (3)) obtained in Example 2 are shown. It should be noted that... Figures 1-2 to 1-5 yes Figure 1-1 A magnified view of the NMR analysis results is shown. Additionally, Figure 2 The results of GC-MS analysis of the alicyclic alcohol (4-isobutyl-2-methylcyclohexyl) methanol (formula (3)) obtained in Example 2 are shown.

[0180] Example 3 (Preparation of alicyclic alcohol ((2-isobutyl-4-methylcyclohexyl)methanol (Formula (4))))

[0181] The aromatic aldehyde mixture obtained in Manufacturing Example 1 was repeatedly distilled using a distillation column with a theoretical number of 80 stages (distillation temperature 150°C, vacuum degree 9 torr) to obtain 2-isobutyl-4-methylbenzaldehyde.

[0182] Using the obtained 2-isobutyl-4-methylbenzaldehyde, the same operation as in Example 1 was performed to obtain (2-isobutyl-4-methylcyclohexyl)methanol (Formula (4)).

[0183] The purity of the obtained (2-isobutyl-4-methylcyclohexyl)methanol (formula (4)) was 92.6% based on the peak area in gas chromatography.

[0184] Figures 3-1 to 3-5 The NMR analysis results of the alicyclic alcohol (2-isobutyl-4-methylcyclohexyl)methanol (formula (4)) obtained in Example 3 are shown. It should be noted that... Figures 3-2 to 3-5 yes Figure 3-1 A magnified view of the NMR analysis results is shown. Additionally, Figure 4 The results of GC-MS analysis of the alicyclic alcohol (2-isobutyl-4-methylcyclohexyl) methanol (formula (4)) obtained in Example 3 are shown.

[0185] <Aroma Evaluation of Alicyclic Alcohol Compositions and Alicyclic Alcohols>

[0186] The aroma of the alicyclic alcohol compositions obtained in Examples 1-3 and each alicyclic alcohol was evaluated. In the aroma evaluation, those with excellent aroma were designated as B, and those with very excellent aroma were designated as A. Details are shown in Table 1.

[0187] Table 1

[0188] Table 1

[0189]

[0190] *) The numbers in the table represent the content (purity) of each compound as a percentage of the peak area in gas chromatography.

[0191] Example 4 and Comparative Examples 1-2 (Sugar Flower Flavoring Composition)

[0192] Five parts by weight of the alicyclic alcohol composition obtained in Example 1 were added to the blended flavoring base (sugar flower flavor) shown in Table 2 to obtain a flavoring composition, and its aroma was evaluated. Furthermore, a flavoring composition obtained by adding 5 parts by weight of dipropylene glycol instead of the alicyclic alcohol composition was used as Comparative Example 1, and its aroma was evaluated in the same manner as the flavoring composition of Example 4, and compared with Example 4. Additionally, a flavoring composition obtained by adding 5 parts by weight of FLOROPAL (2,4,6-trimethyl-4-phenyl-1,3-dioxane, fresh grass, green, floral) instead of the alicyclic alcohol composition was used as Comparative Example 2, and its aroma was evaluated in the same manner as the flavoring composition of Example 4, and compared with Example 4.

[0193] Table 2

[0194]

[0195] Compared with the fragrance compositions of Comparative Examples 1 and 2, the fragrance composition of Example 4 further enhances the sweet and moist feel, the fruity top notes, and the floral middle notes.

[0196] Example 5 and Comparative Examples 3-4 (Rhubarb Flavoring Composition)

[0197] Adding 3 parts by weight of the alicyclic alcohol composition obtained in Example 1 to the blended flavoring base (rhubarb flavor) shown in Table 3 yielded a flavoring composition, which was then evaluated for aroma. Furthermore, a flavoring composition obtained by replacing the alicyclic alcohol composition with 3 parts by weight of dipropylene glycol was selected as Comparative Example 3, and its aroma was evaluated in the same manner as the flavoring composition of Example 5, and compared with Example 5. Additionally, a flavoring composition obtained by replacing the alicyclic alcohol composition with 3 parts by weight of RHUBOFIX (3,4,4a,5,8,8a-hexahydro-3',7-dimethylspiro[1,4-methylenenaphthalene-2(1H),2'-epoxyethylene], with fresh, complex woody, spicy, floral, and fruity aromas of pepper oil) was selected as Comparative Example 4, and its aroma was evaluated in the same manner as the flavoring composition of Example 5, and compared with Example 5.

[0198] Table 3

[0199] Table 3

[0200]

[0201] Compared with the fragrance compositions of Comparative Examples 3 and 4, the fragrance composition of Example 5 has enhanced fruity and floral notes and further improved diffusion.

[0202] As can be seen from the results of Examples 1 to 3, the alicyclic alcohols and alicyclic alcohol compositions of the present invention can be used as fragrances because they have floral and fruity aromas.

[0203] Furthermore, it is known that the alicyclic alcohol compositions of the present invention shown in Examples 4 and 5, compared with FLOROPAL which has other floral aromas and RHUBOFIX which has floral and fruity aromas, can enhance the wateriness and / or enhance the fruity and floral aromas of the fragrance composition, and can bring better diffusion. Therefore, they can also be used as raw materials for blending fragrances.

Claims

1. An alicyclic alcohol composition comprising an alicyclic alcohol of formula (3) and an alicyclic alcohol of formula (4), wherein the ratio of the alicyclic alcohol of formula (3) to the alicyclic alcohol of formula (4) [(3) / (4)] is 80 / 20 to 95 / 5 in terms of peak area ratio in gas chromatography. 。 2. A fragrance composition comprising the alicyclic alcohol composition of claim 1.

Images