WO2022264874A1 - 脂環式アルコール、脂環式アルコール組成物、及び香料組成物 - Google Patents

脂環式アルコール、脂環式アルコール組成物、及び香料組成物 Download PDF

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WO2022264874A1
WO2022264874A1 PCT/JP2022/022904 JP2022022904W WO2022264874A1 WO 2022264874 A1 WO2022264874 A1 WO 2022264874A1 JP 2022022904 W JP2022022904 W JP 2022022904W WO 2022264874 A1 WO2022264874 A1 WO 2022264874A1
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alicyclic alcohol
represented
composition
formula
alicyclic
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French (fr)
Japanese (ja)
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圭祐 戸巻
慎洋 白井
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority to EP22824866.2A priority Critical patent/EP4357329A4/en
Priority to CN202280041270.XA priority patent/CN117480147A/zh
Priority to KR1020237042482A priority patent/KR20240021788A/ko
Priority to US18/569,160 priority patent/US20240279146A1/en
Priority to JP2023529799A priority patent/JPWO2022264874A1/ja
Publication of WO2022264874A1 publication Critical patent/WO2022264874A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/13—Monohydroxylic alcohols containing saturated rings
    • C07C31/133—Monohydroxylic alcohols containing saturated rings monocyclic
    • C07C31/135—Monohydroxylic alcohols containing saturated rings monocyclic with a five or six-membered rings; Naphthenic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/13—Monohydroxylic alcohols containing saturated rings
    • C07C31/133—Monohydroxylic alcohols containing saturated rings monocyclic
    • C07C31/135—Monohydroxylic alcohols containing saturated rings monocyclic with a five or six-membered rings; Naphthenic alcohols
    • C07C31/1355—Monohydroxylic alcohols containing saturated rings monocyclic with a five or six-membered rings; Naphthenic alcohols with a six-membered ring
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
    • A23L27/20—Synthetic spices, flavouring agents or condiments
    • A23L27/203—Alicyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q13/00—Formulations or additives for perfume preparations
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • It relates to an alicyclic alcohol, a method for producing the same, an alicyclic alcohol composition containing the alicyclic alcohol, and a fragrance composition.
  • Non-Patent Document 1 describes that p-isopropylcyclohexylmethanol (mayol) has a floral scent, and p-isopropylcyclohexanol has a floral scent of lilac, rose, geranium with mint added. and that 2,4-dimethyl-3-cyclohexene-1-methanol has a fresh green, floral aroma pronounced of hyacinth and muguet.
  • Non-Patent Document 1 describes that various alicyclic alcohols including these are useful as raw materials for blended fragrances, and describes uses such as skin care products.
  • Patent Document 1 discloses 4-isobutylcyclohexylmethanol and a perfume composition having fresh flower-like, rose-like, citronellal-like, weak Lily of the valley, and osmanthus-like fragrance notes.
  • Alicyclic alcohols used as fragrances are used in various fields such as cosmetics including skin care products as described above, fragrance products, detergents, miscellaneous goods, pharmaceuticals, and foods.
  • the present invention has a floral and fruity scent, and can emphasize juicy, floral, and fruity feelings in addition to the above scents in a mixed perfume, and is useful as a perfume, and can also be used as a raw material for mixed perfumes.
  • An object of the present invention is to provide a useful alicyclic alcohol. Further, another object of the present invention is to provide a method for producing the alicyclic alcohol, an alicyclic alcohol composition containing the alicyclic alcohol, and a perfume composition.
  • the present inventors synthesized and blended various alicyclic alcohols and compositions containing a plurality of them, and evaluated their aromas, and found that specific alicyclic alcohols and compositions containing them have excellent aroma notes Furthermore, the present inventors have found that it is also excellent as a raw material for compounded perfumes, and have completed the present invention.
  • the ratio [(3)/(4)] of the alicyclic alcohol represented by the formula (3) and the alicyclic alcohol represented by the formula (4) is the peak area ratio in the gas chromatograph
  • a method for producing an alicyclic alcohol comprising hydrogenating an aromatic aldehyde represented by the following general formula (5) to obtain an alicyclic alcohol represented by the following general formula (6).
  • the present invention since it has a floral and fruity scent, it is useful as a perfume, and in addition to the above scent, it can emphasize juicy, floral, and fruity feelings in a mixed perfume. can provide cycloaliphatic alcohols that are also useful. Furthermore, a method for producing the alicyclic alcohol, an alicyclic alcohol composition containing the alicyclic alcohol, and a perfume composition can be provided.
  • FIG. 1 is an enlarged view of a part of the NMR analysis results shown in FIG. 1-1.
  • FIG. 1 is an enlarged view of a part of the NMR analysis results shown in FIG. 1-1.
  • FIG. 1 is an enlarged view of a part of the NMR analysis results shown in FIG. 1-1.
  • FIG. 1 is an enlarged view of a part of the NMR analysis results shown in FIG. 1-1.
  • FIG. 1 is an enlarged view of a part of the NMR analysis results shown in FIG. 1-1.
  • FIG. 3 is an enlarged view of a part of the NMR analysis results shown in FIG. 3-1;
  • FIG. 3 is an enlarged view of a part of the NMR analysis results shown in FIG. 3-1;
  • FIG. 3 is an enlarged view of a part of the NMR analysis results shown in FIG. 3-1;
  • FIG. 3 is an enlarged view of a part of the NMR analysis results shown in FIG. 3-1;
  • FIG. 3 is an enlarged view of a part of the NMR analysis results shown in FIG. 3-1;
  • FIG. 3 is an enlarged view of a part of the NMR analysis results shown in FIG. 3-1;
  • FIG. 3 is an enlarged view of a part of the NMR analysis results shown in FIG. 3-1;
  • FIG. 3 is an enlarged view of a part of the NMR analysis results shown in FIG. 3-1;
  • FIG. 3 is an enlarged view of a part of the NMR analysis results shown in FIG. 3-1;
  • FIG. 3 is an enlarged view of a
  • FIG. 3 is an enlarged view of a part of the NMR analysis results shown in FIG. 3-1; It is an example of the GC-MS analysis results of the alicyclic alcohol (2-isobutyl-4-methylcyclohexyl)methanol (formula (4)) of the present invention.
  • alicyclic alcohol The alicyclic alcohol of the present invention is represented by the following general formula (1).
  • the alicyclic alcohol represented by the general formula (1) has a floral and fruity scent and is therefore useful as a perfume. In addition to the above fragrance, it is also useful as a raw material for compounded perfumes because it can emphasize juicy, floral, and fruity sensations.
  • the alicyclic alcohol represented by general formula (1) is preferably obtained by the below-described production method.
  • alicyclic alcohols represented by the general formula (1) alicyclic alcohols represented by the following general formula (2) are preferred.
  • R 1 is a methyl group and R 2 is an isobutyl group, or R 1 is an isobutyl group and R 2 is a methyl group.
  • the alicyclic alcohol represented by the general formula (1) is more preferably an alicyclic alcohol represented by the following formula (3) or an alicyclic alcohol represented by the following formula (4).
  • the alicyclic alcohol represented by the general formula (2) is an alicyclic alcohol represented by the following formula (3) or an alicyclic alcohol represented by the following formula (4).
  • the alicyclic alcohol represented by formula (3) has a floral and fruity scent and is therefore useful as a perfume.
  • it is also useful as a raw material for compounded perfumes because it can emphasize juicy, floral, and fruity sensations.
  • the alicyclic alcohol represented by formula (4) is also useful as a perfume because it has a floral and fruity fragrance.
  • Both the alicyclic alcohol represented by the formula (3) and the alicyclic alcohol represented by the formula (4) are preferably obtained by the production method described below.
  • An alicyclic alcohol composition containing two or more of the alicyclic alcohols represented by the general formula (1) is also preferable because it exhibits the above effects.
  • an alicyclic alcohol composition containing an alicyclic alcohol represented by the following formula (3) and an alicyclic alcohol represented by the following formula (4) is more preferable.
  • the total content of the alicyclic alcohol represented by the formula (3) and the alicyclic alcohol represented by the formula (4) in the alicyclic alcohol composition of the present invention is the peak area ratio in gas chromatography. , preferably 95% or more, more preferably 96% or more, still more preferably 97% or more.
  • the upper limit is not limited, and may be 100% or less.
  • the content of the alicyclic alcohol represented by the formula (3) in the alicyclic alcohol composition of the present invention is preferably 2% or more, more preferably 5% or more, in terms of peak area ratio in gas chromatography. , more preferably 7% or more, still more preferably 70% or more, still more preferably 80% or more, and even more preferably 85% or more. Also, it is preferably 98% or less, more preferably 95% or less, and still more preferably 90% or less.
  • the content of the alicyclic alcohol represented by the formula (4) in the alicyclic alcohol composition of the present invention is preferably 2% or more, more preferably 5% or more, in terms of peak area ratio in gas chromatography. and more preferably 10% or more. Also, it is preferably 98% or less, more preferably 95% or less, still more preferably 93% or less, still more preferably 30% or less, still more preferably 20% or less, and still more Preferably, it is 15% or less.
  • the ratio [(3)/(4)] of the alicyclic alcohol represented by the formula (3) and the alicyclic alcohol represented by the formula (4) in the alicyclic alcohol composition of the present invention is
  • the peak area ratio in gas chromatography is preferably 2/98 to 98/2, more preferably 5/95 to 98/2, still more preferably 7/93 to 98/2, still more preferably 10/90 to 98/2, more preferably 70/30 to 98/2, still more preferably 80/20 to 95/5, still more preferably 85/15 to 90/10 be.
  • the peak area ratio and the peak area ratio in the gas chromatograph are determined by a chromatograph obtained by gas chromatography.
  • chromatography obtained by gas chromatography using a nonpolar column, using an FID as a detector, and measuring at a temperature of 150°C to 300°C. More specifically, it is determined by chromatography measured by the method described in Examples.
  • the alicyclic alcohol composition of the present invention having the above composition has a floral and fruity fragrance, and is therefore useful as a fragrance. Furthermore, in compounded perfumes, juicy, floral, and fruity feelings can be emphasized in addition to the above fragrances, so it is also useful as a raw material for compounded perfumes, and can be used as an aromatic component for various products.
  • the perfume composition of the present invention contains the alicyclic alcohol or the alicyclic alcohol composition. That is, the perfume composition of the first embodiment of the present invention contains an alicyclic alcohol represented by the following general formula (1). Since the fragrance composition of the first embodiment of the present invention contains the alicyclic alcohol having a floral and fruity fragrance, in the blended fragrance (perfume composition), in addition to the fragrance, a juicy feeling, Floral and fruity can be emphasized.
  • the alicyclic alcohol contained in the perfume composition of the first embodiment of the present invention is an alicyclic alcohol represented by the general formula (1), preferably represented by the general formula (2). and more preferably an alicyclic alcohol represented by the above formula (3).
  • the content of the alicyclic alcohol 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 mass. %, more preferably 0.1 to 50% by mass.
  • the perfume composition of the second embodiment of the present invention contains an alicyclic alcohol composition containing two or more of the alicyclic alcohols represented by the general formula (1).
  • the alicyclic alcohol composition contained in the fragrance composition of the second embodiment of the present invention is preferably an alicyclic alcohol represented by the following formula (3) or represented by the following formula (4)
  • a cyclic alcohol composition Since the fragrance composition of the second embodiment of the present invention contains the alicyclic alcohol composition having a floral and fruity fragrance, in the blended fragrance (fragrance composition), in addition to the fragrance, a juicy feeling Also, it can emphasize floral and fruity feelings.
  • the content of the alicyclic alcohol composition in the perfume composition of the present invention may be appropriately adjusted depending on the type of perfume composition, the type and strength of the desired scent, and is preferably 0.01 to 0.01. 90% by mass, more preferably 0.1 to 50% by mass.
  • the "perfume composition of the present invention” in the following description means both the “perfume composition of the first embodiment of the present invention” and the “perfume composition of the second embodiment of the present invention”.
  • the components that can be used in combination with the alicyclic alcohol or the alicyclic alcohol composition are not limited, but the following components can be exemplified. Examples thereof include surfactants, solvents, and perfume substances other than the alicyclic alcohol represented by the general formula (1).
  • surfactants, solvents, and perfume substances other than the alicyclic alcohol represented by the general formula (1) In particular, by combining with a perfume substance other than the alicyclic alcohol represented by the general formula (1), it is possible to impart a floral and fruity scent to the perfume composition, thereby emphasizing the juicy, floral and fruity feeling. .
  • the perfume composition of the present invention preferably contains a perfume substance other than the alicyclic alcohol represented by the general formula (1).
  • Surfactants include polyoxyethylene lauryl sulfate ether and the like.
  • Solvents include dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, triethyl citrate, ethanol and the like.
  • Fragrance substances other than the alicyclic alcohol represented by the general formula (1) that can be used in the fragrance composition of the present invention include hydrocarbons, alcohols, phenols, esters, aldehydes, At least one selected from the group consisting of ketones, acetals, ketals, ethers, nitriles, lactones, natural essential oils, and natural extracts is preferred.
  • perfume substances other than alicyclic alcohols represented by the general formula (1) include hydrocarbons such as limonene, ⁇ -pinene, ⁇ -pinene, terpinene, cedrene, longifolene, and valencene; , citronellol, geraniol, nerol, terpineol, dihydromyrcenol, ethyllinalool, farnesol, nerolidol, cis-3-hexenol, menthol, borneol, ⁇ -phenylethyl 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
  • ketones acetals and ketals of acetaldehyde ethyl phenyl propyl acetal, citral diethyl acetal, phenylacetaldehyde glycerin acetal, ethyl acetoacetate ethylene glycol ketal; anethole, ⁇ -naphthyl methyl ether, ⁇ -naphthyl ethyl ether, limonene oxide, ethers such as rose oxide, 1,8-cineole, racemic or optically active dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan; nitriles such as citronellyl nitrile; - nonalactone, ⁇ -undecalactone, ⁇ - lactones such as decalactone, ⁇ -jasmolactone, coumarin, cyclopentadecanolide, cyclohexa
  • the fragrance composition of the present invention is used for various products such as cosmetics, health and hygiene materials, miscellaneous goods, beverages, foods, quasi-drugs, pharmaceuticals, etc. It can be used as a fragrance ingredient.
  • the fragrance composition of the present invention includes, for example, fragrance products such as perfumes and colognes; hair cosmetics such as shampoos, rinses, hair tonics, hair creams, mousses, gels, pomades and sprays; lotions, serums and creams. , milky lotion, mask, foundation, powder, lipstick, makeup cosmetics, and other skin cosmetics; dishwashing detergent, laundry detergent, household detergent, glass cleaner, softener, bleach, fragrance, insecticide, etc. It can be used as sanitary products; quasi-drugs such as toothpaste, mouthwash, bath powder, antiperspirant, perm agent; miscellaneous goods such as paper products; pharmaceuticals;
  • the content of the perfume composition of the present invention in the above products may be appropriately adjusted depending on the intensity of fragrance required for each product, and is preferably 0.001 to 50% by mass, more preferably 0.001% by mass. 01 to 20% by mass.
  • the alicyclic alcohol of the present invention and the alicyclic alcohol constituting the alicyclic alcohol composition of the present invention may be obtained by any production method.
  • the method for producing an alicyclic alcohol of the present invention preferably hydrogenates an aromatic aldehyde represented by the following general formula (5) to produce an alicyclic alcohol represented by the following general formula (6). is the way to get
  • the aromatic aldehyde represented by the general formula (5) is preferably an aromatic aldehyde represented by the following general formula (7). Therefore, a more preferable method for producing an alicyclic alcohol of the present invention is a method of hydrogenating an aromatic aldehyde represented by the following general formula (7) to obtain an alicyclic alcohol represented by the following general formula (1). is.
  • the aromatic aldehyde represented by the general formula (7) includes aromatic aldehydes represented by the following general formula (7-1) and the like. Furthermore, the aromatic aldehyde represented by the following formula (7-1) is an aromatic aldehyde represented by the following formula (7-2) or an aromatic aldehyde represented by the following formula (7-3). (In the formula, R 1 is a methyl group and R 2 is an isobutyl group, or R 1 is an isobutyl group and R 2 is a methyl group.)
  • the alicyclic alcohol represented by the general formula (2) can be obtained from the aromatic aldehyde represented by the general formula (7-1). Specifically, from the aromatic aldehyde represented by the formula (7-2), the alicyclic alcohol represented by the formula (3) can be obtained, and the aromatic An alicyclic alcohol represented by formula (4) can be obtained from a group aldehyde.
  • the alicyclic alcohol composition containing the alicyclic alcohol represented by the formula (3) and the alicyclic alcohol represented by the formula (4) of the present invention is a raw material represented by the formula (7-2).
  • a mixture of the aromatic aldehyde and the aromatic aldehyde represented by the formula (7-3) may be hydrogenated to directly obtain a composition, or after obtaining each alicyclic alcohol, mixing A composition may be obtained.
  • the aromatic aldehyde represented by the general formula (5) which is the starting material for the hydrogenation reaction, may be obtained by any method. preferably. Formylation in obtaining the aromatic aldehyde represented by the formula (5) used in the production method of the present invention, a method of reacting isobutyltoluene with carbon monoxide in the presence of a superacid is preferred, and specifically, A preferred method is the reaction of isobutyltoluene with carbon monoxide in the presence of a Bronsted acid and a Lewis acid such as , HF/ BF3 .
  • the amount of HF used is preferably 5 to 25 times the molar amount of isobutyltoluene as the raw material, and the amount of BF 3 used is the amount of isobutyltoluene as the raw material. , preferably 0.2 to 2.5 mol times.
  • the reaction temperature is preferably -30 to 10°C.
  • the reaction is preferably carried out under pressure, and the reaction pressure is preferably 1.0-3.0 MPaG.
  • the reaction time is preferably 0.2 to 5 hours.
  • the conditions for the formylation reaction may be adjusted.
  • the ratio may be adjusted by distilling the resulting aromatic aldehyde mixture.
  • an aromatic aldehyde mixture containing an arbitrary ratio of the aromatic aldehyde represented by formula (7-2) and the aromatic aldehyde represented by formula (7-3) can be obtained.
  • the aromatic aldehyde or aromatic aldehyde mixture thus obtained may be used as it is for the hydrogenation reaction, but may be further purified to increase the purity of the desired aromatic aldehyde. Alternatively, it may be separated by distillation or the like, or mixed with another aromatic aldehyde or mixture of aromatic aldehydes to adjust the desired ratio.
  • the reaction conditions for the hydrogenation reaction in the production method of the present invention are not particularly limited, but the aromatic aldehyde or aromatic aldehyde mixture, the hydrogenation catalyst, and, if necessary, a solvent, etc. are placed in a pressure vessel, and hydrogen is added. It is preferable to introduce
  • the hydrogenation catalyst used in this reaction may be any metal catalyst commonly used for hydrogenation, and specific examples thereof include ruthenium catalysts, palladium catalysts, platinum catalysts, cobalt catalysts, and nickel catalysts.
  • At least one selected from the group consisting of a ruthenium catalyst, a palladium catalyst, and a platinum catalyst is preferable, and a ruthenium catalyst is more preferable, from the viewpoint of being able to simultaneously hydrogenate the aldehyde group and the aldehyde group.
  • the metal catalyst carrier include activated carbon, alumina, and diatomaceous earth, with activated carbon being preferred.
  • a solvent may be used in this reaction, 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. In addition, it is preferable not to use a solvent substantially, since the solvent removal process becomes unnecessary.
  • the hydrogen used in this reaction does not have to be particularly refined, and may be of industrial grade.
  • the hydrogen pressure during the reaction is preferably from 2.0 to 20.0 MPa, more preferably from 3.0 to 15.0 MPa, even more preferably from 5.0 to 10.0 MPa.
  • the reaction temperature is preferably 80 to 150°C, more preferably 110 to 140°C. Within this range, side reactions can be suppressed and the desired product can be obtained in high yield, which is preferable.
  • the alicyclic alcohol or alicyclic alcohol composition thus obtained is preferably purified by distillation. Distillation conditions may be appropriately adjusted depending on the pressure and temperature during distillation.
  • the alicyclic alcohol represented by the general formula (1), the alicyclic alcohol represented by the general formula (2), the alicyclic alcohol represented by the formula (3), and the formula (4) ) can be obtained respectively. Further, an alicyclic alcohol composition containing two or more alicyclic alcohols among the alicyclic alcohols represented by the general formula (1), and an alicyclic alcohol represented by the formula (3) and the formula An alicyclic alcohol composition containing both alicyclic alcohols represented by (4) can be obtained. Each of these can be used as a perfume, but they can also be used by mixing them in an arbitrary ratio.
  • an alicyclic alcohol composition containing the alicyclic alcohol represented by the formula (3) and the alicyclic alcohol represented by the formula (4) in the above ratio is preferable to use an alicyclic alcohol composition containing the alicyclic alcohol represented by the formula (3) and the alicyclic alcohol represented by the formula (4) in the above ratio.
  • the obtained alicyclic alcohol represented by the general formula (1) has a floral and fruity fragrance, and is therefore useful as a fragrance. Since it can emphasize a fruity feeling, it is also useful as a raw material for a mixed perfume (perfume composition).
  • composition ratio of alicyclic alcohol and composition ratio of alicyclic alcohol composition The component ratios and composition ratios of the products obtained in the examples were obtained by calculating from the following formulas from the areas of each peak in the chromatograph obtained by the gas chromatography analysis method under the following conditions.
  • the composition ratio ((3)/(4) ratio) of the alicyclic alcohol composition was calculated from the ratio of each alicyclic alcohol in the alicyclic alcohol composition obtained by the following formula.
  • Component ratio (%) of alicyclic alcohol peak area of target alicyclic alcohol/total area of all peaks excluding solvent x 100
  • Ratio (%) of target alicyclic alcohol (alicyclic alcohol represented by formula (3) or alicyclic alcohol represented by formula (4)) in alicyclic alcohol composition target alicyclic alcohol Peak area of cyclic alcohol / sum of peak areas of alicyclic alcohol represented by formula (3) and alicyclic alcohol represented by formula (4) ⁇ 100
  • Production Example 1 production of aromatic aldehyde mixture
  • a 500 mL autoclave equipped with a magnetic drive stirrer, three inlet nozzles at the top, one outlet nozzle at the bottom, and jacketed internal temperature control was used as the formylation reactor.
  • 104.6 g (5.23 mol) of hydrogen fluoride was charged into the autoclave cooled to ⁇ 25° C. by flowing a coolant through the jacket.
  • 79.9 g (1.18 mol) of boron trifluoride was added while stirring and adjusting the temperature not to exceed -25°C.
  • the temperature inside the autoclave was kept at ⁇ 25° C., the pressure was increased to 2 MPaG with carbon monoxide, and 97.8 g (0.66 mol) of m-isobutyltoluene was added.
  • the reaction mixture in the autoclave was drained into ice water. After well shaking the drained material, the oil layer was separated. The obtained oil layer was washed with water to obtain an aromatic aldehyde mixture.
  • Example 1 (Production of alicyclic alcohol composition) A hydrogenation reaction was carried out using the aromatic aldehyde mixture obtained in Production Example 1. 150.0 g of an aromatic aldehyde mixture and 16.5 g of a 5% by mass Ru/C catalyst having a water content of 54.7% (dry weight: 7.5 g) were charged into a 500 mL autoclave, and the interior of the reactor was purged with nitrogen and hydrogen. After that, hydrogen is introduced so that the hydrogen pressure becomes 8.0 MPa, and the reaction is performed for 6 hours while stirring at a reaction temperature of 140 ° C. (the reaction is started when the temperature rise is started), and the alicyclic alcohol composition is obtained. Obtained. The end point of the reaction was the point at which the consumption of hydrogen was completed.
  • the resulting alicyclic alcohol composition was rectified using a rectifying column with 80 theoretical plates (distillation temperature: 132°C, degree of vacuum: 10 torr) to obtain an alicyclic alcohol composition.
  • the resulting alicyclic alcohol composition showed (4-isobutyl-2-methylcyclohexyl)methanol (formula (3)) and (2-isobutyl-4-methylcyclohexyl)methanol (formula (4)) as peaks in gas chromatography. It was an alicyclic alcohol composition containing at an area ratio of 89.1:10.9.
  • Example 2 (Production of alicyclic alcohol ((4-isobutyl-2-methylcyclohexyl)methanol (formula (3)))
  • the aromatic aldehyde mixture obtained in Production Example 1 was repeatedly rectified using a rectifying column with a theoretical plate number of 80 (distillation temperature: 150°C, degree of vacuum: 9 torr) to obtain 4-isobutyl-2-methylbenzaldehyde. Obtained.
  • the purity of the obtained 4-isobutyl-2-methylbenzaldehyde was 98.6% in terms of peak area in gas chromatography. It also contained 0.7% of 2-isobutyl-4-methylbenzaldehyde and 0.7% of other compounds.
  • (4-isobutyl-2-methylcyclohexyl)methanol (formula (3)) was obtained in the same manner as in Example 1 using the obtained 2-isobutyl-4-methylbenzaldehyde.
  • the purity of (4-isobutyl-2-methylcyclohexyl)methanol (formula (3)) thus obtained was 98.0 in peak area in gas chromatography. was 6%.
  • NMR analysis results of the alicyclic alcohol (4-isobutyl-2-methylcyclohexyl)methanol (formula (3)) obtained in Example 2 are shown in Figures 1-1 to 1-5. 1-2 to 1-5 are partially enlarged views of the NMR analysis results shown in FIG. 1-1.
  • GC-MS analysis results of the alicyclic alcohol (4-isobutyl-2-methylcyclohexyl)methanol (formula (3)) obtained in Example 2 are shown in FIG.
  • Example 3 (Production of alicyclic alcohol ((2-isobutyl-4-methylcyclohexyl)methanol (formula (4)))
  • the aromatic aldehyde mixture obtained in Production Example 1 was repeatedly rectified using a rectifying column with a theoretical plate number of 80 (distillation temperature: 150°C, degree of vacuum: 9 torr) to obtain 2-isobutyl-4-methylbenzaldehyde. Obtained.
  • (2-isobutyl-4-methylcyclohexyl)methanol (formula (4)) was obtained in the same manner as in Example 1 using the obtained 2-isobutyl-4-methylbenzaldehyde.
  • the purity of the obtained (2-isobutyl-4-methylcyclohexyl)methanol (formula (4)) was 92.6% in peak area in gas chromatography.
  • NMR analysis results of the alicyclic alcohol (2-isobutyl-4-methylcyclohexyl)methanol (formula (4)) obtained in Example 3 are shown in Figures 3-1 to 3-5. 3-2 to 3-5 are partially enlarged views of the NMR analysis results shown in FIG. 3-1. GC-MS analysis results of the alicyclic alcohol (2-isobutyl-4-methylcyclohexyl)methanol (formula (4)) obtained in Example 3 are shown in FIG.
  • Example 4 and Comparative Examples 1 and 2 sucgar blossom-like perfume composition
  • 5 parts by mass of the alicyclic alcohol composition obtained in Example 1 was added to the blended fragrance base (sugar blossom-like) shown in Table 2 to obtain a fragrance composition, and the fragrance was evaluated.
  • a fragrance composition in which 5 parts by mass of dipropylene glycol was added was used as Comparative Example 1, and the fragrance was evaluated in the same manner as the fragrance composition of Example 4. made a comparison.
  • a fragrance composition in which 5 parts by mass of FLOROPAL (2,4,6-trimethyl-4-phenyl-1,3-dioxane, fresh herbal, green, floral fragrance) is added instead of the alicyclic alcohol composition.
  • the product was used as Comparative Example 2, and the fragrance evaluation was performed in the same manner as the fragrance composition of Example 4, and comparison with Example 4 was performed.
  • Example 4 compared to the perfume compositions of Comparative Examples 1 and 2, the juicy feeling with sweetness, the fruity feeling of the top note, and the floral feeling of the middle note were more emphasized.
  • Example 5 and Comparative Examples 3-4 3 parts by mass of the alicyclic alcohol composition obtained in Example 1 was added to the blended perfume base (rhubarb-like) shown in Table 3 to obtain a perfume composition, which was evaluated for aroma.
  • a fragrance composition in which 3 parts by mass of dipropylene glycol was added instead of the alicyclic alcohol composition was used as Comparative Example 3, and the fragrance was evaluated in the same manner as the fragrance composition of Example 5.
  • Example 5 Comparison with Example 5 did Further, instead of the alicyclic alcohol composition, RHUBOFIX (3,4,4a,5,8,8a-hexahydro-3',7-dimethylspiro[1,4-methanonaphthalene-2(1H),2' -Oxirane], a fresh and complex woody, spicy, floral, fruity scent like pepper oil. Aroma evaluation was performed and comparison with Example 5 was performed.
  • the perfume composition of Example 5 Compared to the perfume compositions of Comparative Examples 3 and 4, the perfume composition of Example 5 emphasized the fruity feeling and the floral feeling, and further improved the diffusibility.
  • the alicyclic alcohol and alicyclic alcohol composition of the present invention are useful as fragrances because they have floral and fruity fragrances.
  • the alicyclic alcohol composition of the present invention is more juicy than other fragrance compositions, such as FLOROPAL having a floral fragrance and RHUBOFIX having a floral and fruity fragrance. It can be used as a raw material for compounded perfumes because it can emphasize the feeling, fruity feeling and floral feeling, and can also impart diffusibility.

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PCT/JP2022/022904 2021-06-14 2022-06-07 脂環式アルコール、脂環式アルコール組成物、及び香料組成物 Ceased WO2022264874A1 (ja)

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EP22824866.2A EP4357329A4 (en) 2021-06-14 2022-06-07 ALICYCLIC ALCOHOL, ALICYCLIC ALCOHOL COMPOSITION AND PERFUME COMPOSITION
CN202280041270.XA CN117480147A (zh) 2021-06-14 2022-06-07 脂环式醇、脂环式醇组合物以及香料组合物
KR1020237042482A KR20240021788A (ko) 2021-06-14 2022-06-07 지환식 알코올, 지환식 알코올 조성물, 및 향료 조성물
US18/569,160 US20240279146A1 (en) 2021-06-14 2022-06-07 Alicyclic alcohol, alicyclic alcohol composition, and perfume composition
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JPH01207252A (ja) 1988-02-12 1989-08-21 Kao Corp ４−イソブチルシクロヘキシルメタノールおよびそれを含有する香料組成物

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CN102256919B (zh) * 2008-12-17 2014-06-25 巴斯夫欧洲公司 生产取代的环己基甲醇的连续方法
JP6963186B2 (ja) * 2016-07-07 2021-11-05 新日本理化株式会社 動力伝達用潤滑油基油

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JPS59225134A (ja) * 1983-06-06 1984-12-18 Towa Kasei Kogyo Kk １−（１−ヒドロキシエチル）−４−イソブチルシクロヘキサンの製造方法
JPH01207252A (ja) 1988-02-12 1989-08-21 Kao Corp ４−イソブチルシクロヘキシルメタノールおよびそれを含有する香料組成物

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DATABASE REGISTRY 23 June 2021 (2021-06-23), ANONYMOUS : "-Cyclohexanemethanol, 2-methyl-4-(2-methylpropyl)- (CA INDEX NAME)", XP093015377, retrieved from STN Database accession no. 2648559-79-7 *
MOTOICHI INDO: "Synthetic Fragrance: Chemistry and Product Knowledge", 1996, THE CHEMICAL DAILY CO. LTD., article "Zoho Kaitei ban, Gosei Koryo: Kagaku to Shohin Chishiki", pages: 54 - 56
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