Perfume, perfume composition, method for producing perfume, and compound

Abstract

Provided are a perfume including a compound useful as a perfume, a perfume composition, and a method for producing the perfume. The perfume includes a compound represented by formula (1) or formula (2). In formulae (1) and (2), R1 and R2 each independently represent a linear, branched, or cyclic C3-C12 alkyl group.

Description

Fragrance, fragrance composition, method for producing fragrance and compound

[0001] The present invention relates to a fragrance, a fragrance composition, a method for producing a fragrance, and a compound.

[0002] Currently, it is known that there are various compounds useful as fragrances. For example, it is known that esters contain compounds useful as fragrances.

[0003] Patent Document 1 describes a fragrance composition that masks unpleasant odors that remain during and after hair coloring treatment, or unpleasant odors that occur when hair is wet after hair coloring treatment.

[0004] Patent Document 2 describes an aromatic floor polish that contains an emulsion containing an acrylic resin and an aromatic component, in which the weight-average molecular weight of the acrylic resin is 100,000 or more.

[0005] Patent Document 3 describes a method for producing an acyloxytetrahydrofuran compound represented by a specific structural formula, which comprises catalytically hydrogenating a compound represented by the specific structural formula using a palladium catalyst in trifluoroacetic acid or in a specific carboxylic acid solution in the coexistence of trifluoroacetic acid.

[0006] Japanese Patent Application Laid-Open No. 2020-196678 Japanese Patent Application Laid-Open No. 2017-8271 Japanese Patent Application Laid-Open No. 57-158774

[0007] In recent years, consumer preferences have become more diverse, and these demands extend to the scent of products. To meet this diversity, there is a demand for the development of novel fragrance ingredients. One embodiment of the present invention aims to provide a fragrance, a fragrance composition, and a method for producing a fragrance, each containing a compound useful as a fragrance. Another embodiment of the present invention aims to provide a novel compound.

[0008] The present invention includes the following embodiments: <1> A fragrance containing a compound represented by formula (1) and / or a compound represented by formula (2). In formula (1) or formula (2), R １and R ２ each independently represents a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms. The alkyl group may contain an unsaturated bond. <2> In the formulas (1) and (2), R １ and R ２ <3> In the formula (1), R １ <4> The fragrance according to <1> or <2>, wherein in the formula (2), R is an n-hexyl group or a 2-ethylhexyl group. ２ is an n-butyl group or an n-hexyl group. <5> A fragrance composition comprising the fragrance according to any one of <1> to <4>. <6> The fragrance composition according to <5>, further comprising at least one fragrance component selected from the group consisting of hydrocarbons having a terpene skeleton, alcohols, phenols, esters, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, hydrocarbons, musks, natural fragrances, natural essential oils, natural extracts, plant extracts, and animal fragrances (excluding those corresponding to the compound represented by formula (1) and / or the compound represented by formula (2)). <7> A method for producing a fragrance, comprising: a furoate production step of reacting 5-methylfurfural with methanol to obtain methyl-5-methylfuran-2-carboxylate; and an interesterified furoate production step of reacting the methyl-5-methylfuran-2-carboxylate with an alcohol to obtain a fragrance containing a compound represented by the following formula (1): In formula (1), R １ represents a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms. １ <9> A method for producing a fragrance according to <7>, wherein represents a linear or branched alkyl group having 3 to 12 carbon atoms. <9> A furoate production step of reacting 5-methylfurfural with methanol to obtain methyl-5-methylfuran-2-carboxylate; ２a hydrogenated furoate producing step of reacting methyl-5-methyltetrahydrofuran-2-carboxylate with an alcohol to obtain a fragrance containing a compound represented by the following formula (2): In formula (2), R ２ represents a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms. ２ <9> A method for producing a fragrance according to <9>, wherein represents a linear or branched alkyl group having 3 to 12 carbon atoms. <11> A compound represented by the following formula (2-1): <12> A compound represented by the following formula (2-2):

[0009] One embodiment of the present invention described above is the embodiments <1> to <10> above, and another embodiment of the present invention described above is the embodiments <11> to <12> above.

[0010] According to one embodiment of the present invention, there are provided a fragrance containing a compound that can be used as a fragrance, a fragrance composition, and a method for producing a fragrance. Also, according to another embodiment of the present invention, there is provided a novel compound.

[0011] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. Note that the following present embodiment is an example for explaining the present invention, and the present invention is not limited to the following embodiment. The present invention can be carried out with appropriate modifications within the scope of its gist. In this embodiment, a numerical range indicated using "to" means a range that includes the numerical values ​​described before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this embodiment, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this embodiment, a combination of two or more preferred aspects is a more preferred aspect. In this embodiment, when multiple substances corresponding to each component are present, the amount of each component refers to the total amount of the multiple substances, unless otherwise specified.

[0012] As used herein, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps, as long as the intended effect of the step is achieved. All steps described herein can be performed in any suitable order unless otherwise specified in the specification or clearly contradicted by the context.

[0013] <Fragrance> The fragrance of the present embodiment includes a compound represented by formula (1) or formula (2). The compound represented by formula (1) or formula (2) can be used as a fragrance component. It has been found that compounds having a methylfurfural structure or a methyltetrahydrofuran structure, such as the compound represented by formula (1) or formula (2), are useful as fragrances, for example, green-like fragrances. Furthermore, it has been found that compounds having a methylfurfural structure or a methyltetrahydrofuran structure and an ester bond can sometimes be used as, for example, a Jasmin-like fragrance. In this embodiment, the use of the compound represented by formula (1) or formula (2) is highly valuable in that, for example, a green-like Jasmin-like fragrance can be obtained from a single compound. Furthermore, the compound represented by formula (1) or formula (2) has high technical value in that such a high-quality fragrance can be obtained despite its relatively small molecular weight. Furthermore, it is also suitable for enhancing palatability when combined with other fragrances.

[0014] <Compound Represented by Formula (1) or Formula (2)> The compound represented by formula (1) or formula (2) will be described in detail below.

[0015]

[0016]

[0017] In formula (1) or formula (2), R １ and R ２ Each of R independently represents a linear, branched, or cyclic alkyl group having 3 to 12 carbon atoms. The alkyl group may contain an unsaturated bond. Preferably, in formulas (1) and (2), R １ and R ２ each independently represents a linear or branched alkyl group having 3 to 12 carbon atoms.

[0018] In formula (1), the linear or branched alkyl group preferably has 4 to 10 carbon atoms, more preferably 5 to 9 carbon atoms, and even more preferably 6 to 8 carbon atoms. In formula (1), the cyclic alkyl group preferably has 5 or 6 carbon atoms. Examples of the alkyl group containing an unsaturated bond include propylene and isobutene. In formula (1), R １ is preferably an n-hexyl group or a 2-ethylhexyl group.

[0019] In formula (2), the linear or branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms. In formula (2), the cyclic alkyl group preferably has 5 or 6 carbon atoms. In formula (2), the alkyl group is preferably linear. In formula (2), R ２ is preferably an n-butyl group or an n-hexyl group.

[0020] The molecular weight of the compound represented by formula (1) or (2) is preferably 140 or more, more preferably 154 or more, and preferably 280 or less, more preferably 266 or less. By making the molecular weight equal to or greater than the lower limit, the fragrance retention tends to be further improved. On the other hand, by making the molecular weight equal to or less than the upper limit, the compound is easily volatilized, making it easier to sense the fragrance. Also, it tends to be less likely to sense a greasy feeling.

[0021] Specific examples of the compounds represented by formula (1) or formula (2) are shown below. It goes without saying that the compounds used in the fragrance of the present embodiment are not limited to the following compounds.

[0022] The content of the compound represented by formula (1) or formula (2) may be 80% by mass or more, 90% by mass or more, or even 100% by mass, based on the total mass of the fragrance.

[0023] <Fragrance Composition> The fragrance composition of the present embodiment contains the fragrance of the present embodiment. The fragrance composition of the present embodiment is not particularly limited in its implementation, as long as it contains the fragrance of the present embodiment. For example, the fragrance composition of the present embodiment may contain other components in addition to the fragrance. The other components may include, for example, other fragrance components (e.g., fragrance components) in addition to the fragrance of the present embodiment.

[0024] Examples of other fragrance components include hydrocarbons having a terpene skeleton or the like, alcohols, phenols, esters, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, hydrocarbons, musks, natural fragrances, natural essential oils or natural extracts, plant extracts, animal fragrances, etc. Furthermore, other fragrance components described in, for example, Fragrance Chemistry Compendium 1, 2, 3 (by Osamu Okuda, published by Hirokawa Shoten), Synthetic Fragrances (by Genichi Indo, published by The Chemical Daily), Japan Patent Office, Collection of Well-Known and Commonly Used Techniques (Fragrances), Part III, Cosmetic Fragrances, p. 26-103, published June 15, 2001, etc. may also be used.

[0025] Specific examples of other fragrance components include hydrocarbons such as limonene, α-pinene, β-pinene, terpinene, cedrene, longifolene, and valencene; linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenol, ethyl linalool, farnesol, nerolidol, cis-3-hexenol, cedrol, menthol, borneol, β-phenylethyl alcohol, benzyl alcohol, phenylhexanol, 2,2,6-trimethylcyclohexyl-3-hexanol, and 1-(2-t-butylcyclohexyloxy)methylcyclohexyl. Alcohols such as 2-butanol, 4-isopropylcyclohexanemethanol, 4-methyl-2-(2-methylpropyl)tetrahydro-2H-pyran-4-ol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, isocamphylcyclohexanol, and 3,7-dimethyl-7-methoxyoctan-2-ol; phenols such as eugenol, thymol, vanillin, and vanitrope;Linalyl formate, citronellyl formate, geranyl formate, n-hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, terpinyl acetate, nopyr acetate, bornyl acetate, isobornyl acetate, o-t-butylcyclohexyl acetate (also known as Floramat (product name)), p-t-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styrallyl acetate, cinnamyl acetate, dimethylbenzylcarbinyl acetate (also known as dimethylbenzylcarbinyl acetate), dimethylbenzylcarbinyl butyrate (also known as dimethylbenzylcarbinyl butyrate), 3-pentyltetrahydropyran-4-yl acetate, citronellol allyl propionate, tricyclodecenyl propionate, allyl cyclohexyl propionate, ethyl 2-cyclohexyl propionate, benzyl propionate, benzyl butyrate (also known as benzyl butyrate), citronellyl butyrate, dimethylbenzyl carbinyl n-butyrate, tricyclodecenyl isobutyrate, methyl 2-nonenoate, methyl benzoate, benzyl benzoate, methyl cinnamate, methyl salicylate, n-hexyl salicylate, cis-3-hexenyl salicylate, geranyl tiglate, cis-3-hexenyl tiglate, methyl jasmonate, methyl dihydrojasmonate, methyl-2,4-dihydroxy-3,6-dimethylbenzoate, ethyl methylphenyl glycidate, methyl anthranilate, fultate and other esters;Aldehydes such as n-octanal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecenal, citronellal, citral, hydroxycitronellal, dimethyltetrahydrobenzaldehyde, 4(3)-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, 2-cyclohexylpropanal, p-t-butyl-α-methylhydrocinnamic aldehyde, p-isopropyl-α-methylhydrocinnamic aldehyde, p-ethyl-α,α-dimethylhydrocinnamic aldehyde, α-amylcinnamic aldehyde, α-hexylcinnamic aldehyde, piperonal, and α-methyl-3,4-methylenedioxyhydrocinnamic aldehyde. amides; methylheptenone, 4-methylene-3,5,6,6-tetramethyl-2-heptanone, amylcyclopentanone, 3-methyl-2-(cis-2-penten-1-yl)-2-cyclopenten-1-one, methylcyclopentenolone, rose ketone, γ-methylionone, α-ionone, carvone, menthone, camphor, nootkatone, benzylacetone, anisylacetone, methyl β-naphthyl ketone, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, maltol, ethyl maltol Ketones such as acetaldehyde, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, muscone, civetone, cyclopentadecanone, and cyclohexadecenone; acetals and ketals such as acetaldehyde ethyl phenylpropyl acetal, citral diethyl acetal, phenylacetaldehyde glycerin acetal, and ethyl acetoacetate ethylene glycol ketals; anethole, β-naphthyl methyl ether, β-naphthyl ethers such as methyl ether, limonene oxide, rose oxide, 1,8-cineole, racemic or optically active dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan; nitriles such as citronellyl nitrile; lactones such as γ-nonalactone, γ-undecalactone, σ-decalactone, γ-jasmolactone, coumarin, cyclopentadecanolide, cyclohexadecanolide, ambrettelide, ethylene brassylate, and 11-oxahexadecanolide;Natural essential oils or natural extracts such as orange, lemon, bergamot, mandarin, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, geranium, jasmine, ylang-ylang, anise, clove, ginger, nutmeg, cardamom, cedar, cypress, vetiver, patchouli, and labdanum; etc. These can be used alone or in combination of two or more.

[0026] Furthermore, the fragrance composition of the present embodiment may contain, if necessary, various additives (which do not function as fragrance components) in addition to the other fragrance components described above. The various additives may be, for example, additives used in cosmetics, health and hygiene materials, daily necessities, miscellaneous goods, fibers, textile products, clothing, foods, quasi-drugs, pharmaceuticals, etc.

[0027] Specific examples of various additives include solvents and / or dispersion media such as dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, and triethyl citrate, powders, liquid oils and fats, solid oils and fats, wax, oil-soluble components, silicones, hydrocarbons, higher fatty acids, higher alcohols, lower alcohols, polyhydric alcohols, esters, glycols, alcohol ethers, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, anionic surfactants such as polyoxyethylene lauryl sulfate ether, cationic surfactants, amphoteric surfactants, nonionic surfactants, UV absorbers, oil gelling agents, moisturizers, aqueous components, propellants, antioxidants, antioxidant aids, cosmetic ingredients, preservatives, water-soluble polymers, water, film-forming agents, anti-fading agents, fragrance retention agents, thickeners, antifoaming agents, disinfectants, deodorizers, dyes, pigments, pearlizing agents, chelating agents, and gelling agents. These may be used alone or in combination of two or more.

[0028] The fragrance composition of this embodiment can be used in any form depending on the various additives to be blended. The fragrance composition of this embodiment can be used, for example, in the form of a liquid, gel, semi-solid, gel, solid, powder, mist, aerosol, emulsion, or suspension. The fragrance composition of this embodiment can also be used in the form of being sprayed, applied, adsorbed, mixed, dispersed, emulsified, kneaded, supported, penetrated, or impregnated onto substrates such as organic or inorganic fibers (e.g., yarn, woven or knitted fabric, woven fabric, nonwoven fabric, paper), resin, clothing material, or clothing. Furthermore, the fragrance composition of this embodiment can also be applied using microcapsules or the like. The fragrance of the fragrance and fragrance composition of this embodiment can also be sprayed or diffused using a diffuser.

[0029] The content of the compound represented by formula (1) or formula (2) in the fragrance composition of this embodiment can be appropriately set depending on the type and intensity of the desired fragrance, the types and amounts of other fragrance components used in combination, the desired fragrance duration, the form of use, etc. The content of the compound represented by formula (1) or formula (2) in the fragrance composition of this embodiment is preferably 0.01% by mass to 90% by mass, and more preferably 0.1% by mass to 50% by mass, relative to the total amount of the fragrance composition.

[0030] [Uses] The uses of the fragrance composition of the present embodiment are not particularly limited, but suitable examples include cosmetics, food additives, and detergents.

[0031] The fragrance of the present embodiment can be widely used alone or as a blended fragrance ingredient as a fragrance component (fragrance-imparting component) for various products, such as cosmetics, health and hygiene materials, daily necessities, miscellaneous goods, textiles, textile products, clothing, foods, quasi-drugs, and pharmaceuticals, and can also be used to improve the fragrance of the product to be blended.

[0032] Specific examples of various products include fragrance products, basic cosmetics, finishing cosmetics, hair cosmetics, hair cosmetics, skin cosmetics, suntan cosmetics, medicated cosmetics, soap, body cleansers, bath additives, detergents, fabric softeners, bleaches, disinfectant detergents, deodorizing detergents, furniture care, various cleaning agents, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, aerosols, deodorizers, air fresheners, deodorizing air fresheners, repellents, and other miscellaneous goods.

[0033] More specifically, for example, perfume, parfum, eau de parfum, eau de toilette, colognes, fragrance powder, solid perfume, shampoo, conditioner, rinse, rinse-in shampoo, hair tonic, hair cream, Brilantine, setting lotion, hair stick, hair solid, hair oil, hair mousse, hair gel, hair pomade, hair liquid, hair spray, hair color, hair pack, hair tonic, hair dye, lotion, emulsion, body lotion, body powder, body soap, hand soap, hand cream Body cream, aroma oil, serum, cream, emulsion, mask, foundation, powder, lipstick, facial cleanser, face wash, makeup remover, mask, vanishing cream, cleansing cream, cold cream, massage cream, oil blotting paper, foundation, eye shadow, eyeliner, mascara, lipstick, primer, powder powder, solid powder, talcum powder, lip balm, blush, eyebrow pencil, eye mask, nail enamel, enamel remover, cosmetic soap, bath soap, perfumed soap, transparent soap, synthetic soap, liquid soap, bath soap (bath tablets, bath liquid, foam bath, bath oil, bath capsules), milk bath, bath jelly, bath cube, antiperspirant, lip balm, shaving foam, aftershave lotion, shaving gel, hair growth lotion, permanent wave agent, medicated soap, medicated shampoo, medicated skin care products, dishwashing detergent, kitchen detergent, dishwashing detergent, laundry detergent, heavy-duty laundry detergent, light-duty laundry detergent, liquid detergent, compact detergent, powdered soap, softeners, furniture care, disinfectant detergents, deodorizing detergents, drain cleaners, oxidative bleach agents, reduced bleaching agents, optical bleaching agents, aerosol agents, solid / gel / liquid deodorizers, solid / gel / liquid air fresheners, solid / gel / liquid deodorizing air fresheners, cleansers, glass cleaners, furniture cleaners, leather cleaners, floor cleaners, house cleaners, textile cleaners, leather cleaners, toilet cleaners, bathroom cleaners, glass cleaners, mold removers, furniture care, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, toothpaste, mouthwash, bath additives, antiperspirant products, sunscreen creams, perm solution, hair removal agents,Examples of such products include ointments, poultices, patches, hair growth agents, mouthwashes, toilet paper, tissue paper, scented paper, room fragrances, aroma candles, and aroma oils.

[0034] <<Method for Producing Fragrance>> The method for producing a fragrance of the present embodiment includes a production method A for obtaining a fragrance containing a compound represented by formula (1) and a production method B for obtaining a fragrance containing a compound represented by formula (2).

[0035] <Production Method A> Production method A includes a furoate production step of reacting 5-methylfurfural with methanol to obtain methyl-5-methylfuran-2-carboxylate, and a transesterified furoate production step of reacting the methyl-5-methylfuran-2-carboxylate with an alcohol to obtain a fragrance containing a compound represented by the following formula (1):

[0036]

[0037] In formula (1), R １ represents a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms. １ represents a linear or branched alkyl group having 3 to 12 carbon atoms.

[0038] (Furoate Production Step) The furoate production step is a step in which 5-methylfurfural is reacted with methanol to obtain methyl-5-methylfuran-2-carboxylate.

[0039] The content of methanol relative to 5-methylfurfural is preferably 1.0% by mass to 10.0% by mass, more preferably 2.0% by mass to 7.0% by mass, and even more preferably 2.5% by mass to 4.5% by mass.

[0040] In the furoate production step, methanol may be the solvent.

[0041] The furoate production process may be carried out using, for example, a catalyst (e.g., NaCN) and an oxidizing agent (e.g., MnO ２) may be used to react 5-methylfurfural with methanol to obtain methyl-5-methylfuran-2-carboxylate. Specifically, 5-methylfurfural may be reacted with a catalyst, and then oxidized with an oxidizing agent.

[0042] In the reaction between 5-methylfurfural and the catalyst, the reaction time is not particularly limited, but is preferably 3 to 30 minutes, more preferably 5 to 20 minutes, and even more preferably 7 to 15 minutes.

[0043] In the reaction between 5-methylfurfural and the catalyst, the reaction temperature is not particularly limited, but is preferably 15 to 60°C, more preferably 20 to 40°C.

[0044] In the reaction between 5-methylfurfural and the catalyst, the stirring speed is not particularly limited, but is preferably 100 rpm to 500 rpm, and more preferably 200 rpm to 400 rpm.

[0045] In the oxidation reaction using an oxidizing agent, the reaction time is not particularly limited, but is preferably 1 to 10 hours, more preferably 2 to 8 hours, and even more preferably 3 to 6 hours.

[0046] In the oxidation reaction using an oxidizing agent, the reaction temperature is not particularly limited, but is preferably 1°C to 60°C, and more preferably 2°C to 50°C.

[0047] In the oxidation reaction using an oxidizing agent, the stirring speed is not particularly limited, but is preferably 100 rpm to 500 rpm, and more preferably 200 rpm to 400 rpm.

[0048] The furoate production step may be carried out, for example, by the following method. As shown in the following reaction formula, 5-methylfurfural, NaCN as a catalyst, and methanol as a solvent are mixed and stirred at 25°C for 10 minutes at 300 rpm (revolutions per minute). After confirming that NaCN has dissolved, the reaction solution is cooled and kept at 2°C to 10°C while stirring NaCN. ２ CO３ and MnO ２ The reaction mixture was then heated to 40°C and the reaction was carried out.

[0049]

[0050] (Transesterification Furoate Production Step) The transesterification furoate production step is a step in which methyl-5-methylfuran-2-carboxylate is reacted with an alcohol to obtain a fragrance containing a compound represented by the following formula (1).

[0051] The alcohol may be, for example, a linear or branched alcohol having 3 to 12 carbon atoms. The alcohol preferably has 4 to 10 carbon atoms, more preferably 5 to 9 carbon atoms, and even more preferably 6 to 8 carbon atoms. The alcohol is preferably n-hexanol or 2-ethylhexanol.

[0052] The content of the alcohol relative to methyl-5-methylfuran-2-carboxylate is preferably 1.0 to 5.0 molar equivalents, more preferably 1.5 to 4.0 molar equivalents, and even more preferably 2.0 to 3.5 molar equivalents.

[0053] In the step of producing transesterified furoate, a catalyst may be used. Examples of the catalyst include inorganic acids such as sulfuric acid, phosphoric acid, and hydrochloric acid, and organic sulfonic acids such as paratoluenesulfonic acid, benzenesulfonic acid, and methanesulfonic acid. Among these, paratoluenesulfonic acid is preferred as the catalyst.

[0054] The content of the catalyst relative to methyl-5-methylfuran-2-carboxylate is preferably 1% by mass to 10% by mass, more preferably 2% by mass to 7% by mass, and even more preferably 3% by mass to 6% by mass.

[0055] In the transesterified furoate production step, the reaction time is not particularly limited, but is preferably 1 to 10 hours, more preferably 2 to 8 hours, and even more preferably 3 to 6 hours.

[0056] In the transesterified furoate production step, the reaction temperature is not particularly limited, but is preferably 60°C to 250°C, and more preferably 100°C to 200°C.

[0057] In the transesterified furoate production step, the stirring speed is not particularly limited, but is preferably 300 rpm to 800 rpm, and more preferably 400 rpm to 700 rpm.

[0058] The transesterified furoate production step may be carried out, for example, by the following method. As shown in the following reaction formula, the methyl-5-methylfuran-2-carboxylate prepared above, an alcohol, and p-toluenesulfonic acid as a catalyst are mixed in a two-necked flask, and the reaction is carried out at 150°C for 4 hours at 500 rpm. Methanol, which is a by-product of the reaction, may be removed from the system during the reaction.

[0059]

[0060] <Production Method B> Production Method B includes a furoate production step of reacting 5-methylfurfural with methanol to obtain methyl-5-methylfuran-2-carboxylate, and a hydrogen ion reaction step of reacting the methyl-5-methylfuran-2-carboxylate with H. ２ and a transesterified hydrogenated furoate production step of reacting methyl-5-methyltetrahydrofuran-2-carboxylate with an alcohol to obtain a fragrance containing a compound represented by the following formula (2):

[0061]

[0062] In formula (2), R ２ represents a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms. ２ represents a linear or branched alkyl group having 3 to 12 carbon atoms.

[0063] (Furoate Production Step) The furoate production step is a step in which 5-methylfurfural is reacted with methanol to obtain methyl-5-methylfuran-2-carboxylate. Details of the specific aspects, preferred aspects, etc. of the furoate production step in Production Method B are the same as the details of the specific aspects, preferred aspects, etc. of the furoate production step in Production Method A described above.

[0064] (Hydrogenated Furoate Production Step) The hydrogenated furoate production step is carried out by reacting the methyl-5-methylfuran-2-carboxylate with H ２ to obtain methyl-5-methyltetrahydrofuran-2-carboxylate.

[0065] A catalyst may be used in the hydrogenated furoate production step. Examples of the catalyst include hydrogenation catalysts. Examples of the hydrogenation catalyst include metal powders, complexes, and oxide powders of Group 8 metals such as palladium, platinum, ruthenium, rhodium, iridium, cobalt, and nickel, as well as supported catalysts in which the Group 8 metals are supported on a support such as activated carbon, silica gel, or alumina. In the supported catalysts, the content of the Group 8 metal relative to the total mass of the support is not particularly limited, but may be 0.5% by mass to 20% by mass. Among these, preferred hydrogenation catalysts are rhodium supported on activated carbon, ruthenium supported on activated carbon, ruthenium supported on alumina, rhodium supported on alumina, and Raney nickel.

[0066] The content of the catalyst relative to methyl-5-methylfuran-2-carboxylate is preferably 1% by mass to 15% by mass, more preferably 3% by mass to 10% by mass, and even more preferably 4% by mass to 8% by mass.

[0067] In the hydrogenated furoate production step, the reaction pressure is preferably 1.0 MPa to 15.0 MPa, more preferably 2.0 MPa to 10.0 MPa, and even more preferably 3.0 MPa to 7.0 MPa.

[0068] In the hydrogenated furoate production step, the reaction time is not particularly limited, but is preferably 1 to 15 hours, more preferably 3 to 12 hours, and even more preferably 5 to 10 hours.

[0069] In the hydrogenated furoate production step, the reaction temperature is not particularly limited, but is preferably 50°C to 200°C, and more preferably 70°C to 120°C.

[0070] The hydrogenated furoate production step may be carried out, for example, by the following method. As shown in the reaction formula below, the above-prepared methyl-5-methylfuran-2-carboxylate and a 5% Rh / C catalyst are charged into an autoclave, and after purging with nitrogen gas three times, an airtightness test is carried out at 6 MPa. After the pressure is reduced, H ２ The system is pressurized with gas, and the reaction is carried out at 90° C. and 4.5 MPa for 7.5 hours to obtain the target methyl-5-methyltetrahydrofuran-2-carboxylate.

[0071]

[0072] <Compound> The compound of this embodiment is a compound represented by the following formula (2-1).

[0073]

[0074] Another example of the compound of this embodiment is a compound represented by the following formula (2-2).

[0075] The compound of this embodiment is a novel compound and can be used as a fragrance ingredient. A fragrance composition containing the compound of this embodiment exhibits smooth floral and natural diffusibility.

[0076] Hereinafter, the present embodiment will be described in more detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples in any way.

[0077] The measurement method in this example is as follows. <Gas chromatography analysis conditions> Analytical apparatus: Capillary gas chromatograph GC-2014 manufactured by Shimadzu Corporation Analytical column: HP-5 (30 m, 0.32 mm I.D., film thickness 0.25 μm) manufactured by GL Sciences Inc. Oven temperature: 50°C (5 minutes) - heating rate 20°C / min - 280°C (14.5 minutes) Detector: FID, temperature 280°C

[0078] <GC-MS measurement conditions> Analytical device: GCMS-7890 / 5975 manufactured by Agilent Technologies Ionization voltage: 70 eV Analytical column: DB-5MS UI manufactured by Agilent Technologies (30 m, 0.25 mm I.D., film thickness 0.25 μm) Oven temperature: 50° C. (0 min) - heating rate 5° C. / min - 150° C. (0 min) - heating rate 20° C. / min - 320° C. (5 min)

[0079] <1H-NMR Spectroscopic Analysis> Apparatus: Bruker 1H-NMR spectrometer AVANCE NEO 500 MHz Internal standard substance: tetramethylsilane (TMS)

[0080] <Yield and Selectivity> The area percentage (GC%) of the target product was determined by gas chromatography analysis, and the yield and selectivity of the target product were calculated by the internal standard method using the following formulas: Yield (mol %) = Amount of target product obtained (mol) / Amount of raw material charged (mol) × 100 Selectivity (mol %) = Amount of target product obtained (mol) / Amount of raw material reacted (mol) × 100

[0081] <Synthesis Example 1> (Method for synthesizing methyl-5-methylfuran-2-carboxylate [furoate formation step])

[0082]

[0083] A 1000 mL three-neck flask equipped with a mechanical stirrer, a thermometer, and an exhaust gas line was charged with 66.0 g of 5-methylfurfural, 1.176 g of NaCN as a catalyst, and 214.0 g of methanol as a solvent, and the mixture was stirred at 25°C for 10 minutes at 300 rpm (revolutions per minute). After confirming that NaCN had dissolved, the reaction solution was cooled and, while maintaining the temperature at 2 to 10°C, Na ２ CO ３ 31.8 g and MnO ２ 188.0 g of the reaction mixture was added little by little over 20 to 30 minutes. The reaction mixture was heated to 40° C. and reacted for 4 hours at 300 rpm.

[0084] After cooling the reaction mixture, the mixture was subjected to solid-liquid separation and rinsed five times with 40 mL of methanol. 434.8 g of the resulting mixture was analyzed by gas chromatography using the internal standard method. The analysis revealed that it contained 80.7 g of the target methyl-5-methylfuran-2-carboxylate. The yield was 96.1 mol %, and the selectivity was 96.1 mol %. The resulting mixture was rectified using a rectification column with five theoretical plates (distillation temperature 61°C, vacuum degree 0.4 kPa). 75.9 g of a main fraction with a GC% of 99.0% was obtained by gas chromatography (distillation yield 94.0 mol %). GC-MS analysis of the resulting fraction showed that the molecular weight of the target compound was 140. Furthermore, the chromatographic analysis of the fraction in deuterated chloroform solvent revealed that the target compound was methyl-5-methylfuran-2-carboxylate. １ The H-NMR chemical shift values ​​(δ ppm, TMS standard) were 2.38 (s, 3H), 3.87 (s, 3H), 6.12 (d, 1H), and 7.08 (d, 1H), which identified the target compound as methyl-5-methylfuran-2-carboxylate.

[0085] <Synthesis Example 2> (Method for synthesizing methyl-5-methyltetrahydrofuran-2-carboxylate [hydrogenated furoate formation step])

[0086]

[0087] The hydrogenation reaction was carried out using a 75 mL stainless steel autoclave equipped with a magnetic induction stirrer and three inlet nozzles at the top. 49.0 g of the methyl-5-methylfuran-2-carboxylate prepared above and 3.0 g of a 5% Rh / C catalyst (water content: 50.5% by mass) were charged into the autoclave, and the autoclave was purged with nitrogen gas three times. After that, an airtightness test was carried out at 6 MPa. After the pressure was reduced, H ２ The system was pressurized with gas, and the reaction was carried out at 90°C and 4.5 MPa for 7.5 hours. After the reaction was completed, solid-liquid separation was performed, and the mixture was rinsed three times with 10 mL of methanol. 73.4 g of the resulting liquid was analyzed by gas chromatography using the internal standard method, and it was found to contain 45.4 g of the target methyl-5-methyltetrahydrofuran-2-carboxylate. The yield was 90.0 mol %, and the selectivity was 90.0 mol %. The resulting liquid was rectified using a rectification column with five theoretical plates (distillation temperature 48°C, vacuum degree 0.2 kPa), and 41.2 g of a main fraction with a gas chromatographic analysis of 99.1 GC% was obtained (distillation yield 92.0 mol %). The resulting fraction was analyzed by GC-MS, and the molecular weight of the target product was 144. Furthermore, the chromatographic analysis of the resulting fraction in deuterated chloroform solvent was also found to be 90.0 mol %. １ The H-NMR chemical shift values ​​(δ ppm, TMS standard) were 1.34 (d, 3H), 1.53 (m, 1H), 2.01 (m, 1H), 2.10 (m, 1H), 2.23 (m, 1H), 3.74 (s, 3H), 4.19 (m, 1H), and 4.49 (m, 1H). This identified the product as methyl-5-methyltetrahydrofuran-2-carboxylate.

[0088] Example 1 (Method for synthesizing 1-hexyl-5-methyltetrahydrofuran-2-carboxylate [Transesterified hydrogenated furoate production step])

[0089]

[0090] A 100 mL two-neck flask equipped with a Dean-Stark apparatus, a thermometer, and a stirrer was charged with 20.1 g of the methyl 5-methyltetrahydrofuran-2-carboxylate prepared above, 35.6 g of 1-hexanol (2.5-fold molar equivalent relative to the substrate), and 0.80 g of p-toluenesulfonic acid as a catalyst (4% by mass relative to the substrate), and the reaction was carried out at 150°C for 4 hours at 500 rpm. During the reaction, methanol, a by-product of the reaction, was removed from the system. After completion of the reaction, the mixture was washed once with 20 mL of 0.2% by mass aqueous NaOH solution and twice with 20 mL of distilled water. Analysis of 49.9 g of the resulting liquid by gas chromatography using the internal standard method revealed that it contained 27.5 g of the target 1-hexyl-5-methyltetrahydrofuran-2-carboxylate. The yield was 92.0 mol %, and the selectivity was 94.4 mol %. The resulting liquid was rectified using a rectification column with five theoretical plates (distillation temperature 75°C, vacuum 0.13 kPa), and 25.0 g of a main fraction with a GC% of 98.9% was obtained by gas chromatography (distillation yield 91.0 mol%). The obtained fraction was analyzed by GC-MS, and the molecular weight of the target compound was 214. Furthermore, in a deuterated chloroform solvent, １ The H-NMR chemical shift values ​​(δ ppm, TMS standard) were 0.88 (t, 3H), 1.30 (m, 6H), 1.34 (d, 3H), 1.60 (m, 3H), 2.16 (m, 3H), 4.25 (m, 3H), and 4.47 (q, 1H). This identified the compound as 1-hexyl-5-methyltetrahydrofuran-2-carboxylate [compound represented by formula (2-1)].

[0091] The obtained fraction has a novel, attractive jasmine-like floral fragrance with a herbal feel, unlike the known fructose, which has only a fruity fragrance, or the known geranyl acetate, which has only a rose-like fragrance, and is characterized by superior fragrance persistence compared to other known esters or geranyl acetate.

[0092] (Fragrance composition that can impart a natural feel and natural green notes to a white floral scent) A comparison was made using a Gardenia-type formulation with CIS-3-HEXENYL BENZOATE as a benchmark. 1-Hexyl-5-methyltetrahydrofuran-2-carboxylate was used in the formulation at 3% by mass (CIS-3-HEXENYL BENZOATE: 97 g, 1-Hexyl-5-methyltetrahydrofuran-2-carboxylate: 3 g). In a fragrance evaluation by a perfumer, the resulting fragrance composition exhibited a fairly strong metallic, sharp green feel even in Gardenia, while also expressing a smooth, natural note with a sharp edge. Over time, a soft jasmine tone with the texture of white floral petals emerged. 1-Hexyl-5-methyltetrahydrofuran-2-carboxylate transforms the slightly sweet and flat fragrance of Gardenia into a more natural, deep floral scent. It was confirmed that the natural-feeling green lingering scent matches the fragrance of Gardenia and enhances its palatability.

[0093] Example 2 (Method for synthesizing 1-butyl-5-methyltetrahydrofuran-2-carboxylate [Transesterified hydrogenated furoate production step])

[0094]

[0095] Synthesis and distillation were carried out in the same manner as in Example 1, except that 1-butanol was used instead of 1-hexanol. The obtained fraction was analyzed by GC-MS, and the molecular weight of the target compound was 186. Furthermore, in a deuterated chloroform solvent, １ The H-NMR chemical shift values ​​(δ ppm, TMS standard) were 0.93 (t, 3H), 1.30 (d, 3H), 1.50 (m, 5H), 2.15 (m, 3H), 4.20 (m, 3H), and 4.47 (m, 1H). This identified the target compound, 1-butyl-5-methyltetrahydrofuran-2-carboxylate [compound represented by formula (2)].

[0096] The obtained fraction was characterized by a novel fragrance with a green, jasmine-like floral and fruity element, unlike the known fructose, which has only a fruity fragrance, or the known geranyl acetate, which has only a rose-like fragrance.

[0097] (Fragrance composition imparting a smooth floral feel and natural diffusibility) VELOUTONE was used as a benchmark for comparison in an Osmanthus-type formulation. 2% by mass of 1-butyl-5-methyltetrahydrofuran-2-carboxylate was used in the formulation (VELOUTONE: 98 g, 1-butyl-5-methyltetrahydrofuran-2-carboxylate: 2 g). In a fragrance evaluation by a perfumer, the resulting fragrance composition was found to have a woody characteristic of Osmanthus fragrance, and VELOUTONE tended to have a somewhat subdued overall tone. However, 1-butyl-5-methyltetrahydrofuran-2-carboxylate shifted the woody note to a smooth floral feel, resulting in a more expansive fragrance. The lingering fragrance also imparted the body of a Jasmin floral, confirming that it is a highly effective ingredient for floral fragrances.

[0098] Example 3 (Method for synthesizing 1-hexyl-5-methylfuran-2-carboxylate [Transesterified furoate production step])

[0099]

[0100] Synthesis and distillation were carried out in the same manner as in Example 1, except that methyl-5-methylfuran-2-carboxylate was used instead of methyl-5-methyltetrahydrofuran-2-carboxylate. The obtained fraction was analyzed by GC-MS, and the molecular weight of the target compound was 210. Furthermore, in deuterated chloroform solvent, １The H-NMR chemical shift values ​​(δ ppm, TMS standard) were 0.89 (t, 3H), 1.36 (m, 6H), 1.72 (tt, 2H), 2.38 (s, 3H), 4.27 (t, 2H), 6.10 (d, 1H), and 7.06 (d, 1H). This identified the target compound, 1-hexyl-5-methylfuran-2-carboxylate [compound represented by formula (1)].

[0101] The obtained fraction had a novel CIS-3-SALICYLATE-like fragrance with a strong floral feel, unlike known fultate, which has only a fruity fragrance, or known geranyl acetate, which has only a rose-like fragrance, and was characterized by superior fragrance persistence compared to other known esters or geranyl acetate.

[0102] (A fragrance composition that imparts a natural feel to a white floral scent and a green note to the lingering fragrance.) CIS-3-HEXENYL SALICYLATE was used as a benchmark for comparison in the formulation of a Hand & Body Lotion. 30% by mass of 1-hexyl-5-methylfuran-2-carboxylate was used in the formulation (CIS-3-HEXENYL SALICYLATE: 70 g, 1-hexyl-5-methylfuran-2-carboxylate: 30 g). In a fragrance evaluation by a perfumer, the resulting fragrance composition gave an overall impression of a soft, elegant floral-green. After one day, it was confirmed that the material exuded a floral feel reminiscent of natural flower petals, unlike the effect of CIS-3-HEXENYL SALICYLATE.

[0103] Example 4 (Method for synthesizing 2-ethylhexyl-5-methylfuran-2-carboxylate [Transesterified furoate production step])

[0104]

[0105] Synthesis and distillation were carried out in the same manner as in Example 3, except that 2-ethylhexanol was used instead of 1-hexanol. The obtained fraction was analyzed by GC-MS, and the molecular weight of the target compound was 238. Furthermore, in deuterated chloroform solvent, １The H-NMR chemical shift values ​​(δ ppm, TMS standard) were 0.91 (m, 6H), 1.36 (m, 8H), 1.68 (ttt, 1H), 2.38 (s, 3H), 4.19 (dd, 2H), 6.10 (d, 1H), and 7.04 (d, 1H). This identified the target compound, 1-ethylhexyl-5-methylfuran-2-carboxylate [compound represented by formula (1)].

[0106] The obtained fraction differed from the known fructose, which has only a fruity fragrance, or the known geranyl acetate, which has only a rose-like fragrance, in that it had a soft, green floral and balsamic aroma, and had a novel, very high-quality benzyl salicylate-like fragrance, and the fragrance persistence was superior to that of other known esters or geranyl acetate.

[0107] (Fragrance composition that can impart diffusibility with a white floral feel and a natural feel) A Jasmin-type formulation was compared with BENZYL SALICYLATE as a benchmark. 10% by mass of 1-ethylhexyl-5-methylfuran-2-carboxylate was used in the formulation (BENZYL SALICYLATE: 90 g, 1-ethylhexyl-5-methylfuran-2-carboxylate: 10 g). In a fragrance evaluation by a perfumer, the resulting fragrance composition was found to have enhanced the animalic and cheap image with an elegant floral feel, while also imparting a smooth natural feel. Over time, the texture of Jasmin's white petals is skillfully expressed. It was confirmed that the fatty, natural-feeling lingering fragrance is a material that enhances the texture by luxuriously presenting Jasmin's base note.

[0108] Comparative Example 1 (Method for synthesizing ethyl-5-methylfuran-2-carboxylate)

[0109]

[0110] Except for using ethanol instead of 1-hexanol, synthesis and distillation were carried out in the same manner as in Example 3. Analysis of the obtained fraction by GC-MS showed that the molecular weight of the target product was 154, and it was identified as 1-ethyl-5-methylfuran-2-carboxylate.

[0111] The resulting fraction had a pungent, fatty green note. The lingering scent was weak and the characteristics were unclear, so it was determined that it would be difficult to use as a fragrance.

[0112] Example 5 (Method for synthesizing 2-ethylhexyl-5-methyltetrahydrofuran-2-carboxylate [Transesterified furoate production step])

[0113] Synthesis and distillation were carried out in the same manner as in Example 1, except that 2-ethylhexanol was used instead of 1-hexanol. The obtained fraction was analyzed by GC-MS, and the molecular weight of the target compound was 242. Furthermore, in a deuterated chloroform solvent, １ The H-NMR chemical shift values ​​(δ ppm, TMS standard) were 0.89 (m, 6H), 1.34 (m, 10H), 1.59 (m, 3H), 2.13 (m, 3H), 4.07 (m, 3H), and 4.43 (q, 1H). This identified the target compound as 2-ethylhexyl-5-methyltetrahydrofuran-2-carboxylate [compound represented by formula (3)].

[0114] The fragrance of this embodiment contains compounds useful as fragrances, and is therefore useful as a fragrance ingredient in a wide range of products.

Claims

1. A fragrance containing a compound represented by formula (1) and / or a compound represented by formula (2). In formula (1) or formula (2), R １ and R ２ each independently represents a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms. The alkyl group may contain an unsaturated bond.

2. In the above formulas (1) and (2), R １ and R ２ Each of the radicals independently represents a linear or branched alkyl group having 3 to 12 carbon atoms.

3. In the formula (1), R １ The fragrance according to claim 1, wherein is an n-hexyl group or a 2-ethylhexyl group.

4. In the formula (2), R ２ The fragrance according to claim 1 or 2, wherein is an n-butyl group or an n-hexyl group.

5. A fragrance composition comprising the fragrance according to claim 1 or 2.

6. The fragrance composition according to claim 5, further comprising at least one fragrance component selected from the group consisting of hydrocarbons having a terpene skeleton, alcohols, phenols, esters, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, hydrocarbons, musks, natural fragrances, natural essential oils, natural extracts, plant extracts, and animal fragrances (excluding those corresponding to the compound represented by formula (1) and / or the compound represented by formula (2)).

7. A method for producing a fragrance, comprising: a furoate production step of reacting 5-methylfurfural with methanol to obtain methyl-5-methylfuran-2-carboxylate; and an ester-exchange furoate production step of reacting the methyl-5-methylfuran-2-carboxylate with an alcohol to obtain a fragrance containing a compound represented by the following formula (1): In formula (1), R １ represents a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms.

8. In formula (1), R １ The method for producing a fragrance according to claim 7, wherein represents a linear or branched alkyl group having 3 to 12 carbon atoms.

9. A furoate production process in which 5-methylfurfural is reacted with methanol to obtain methyl-5-methylfuran-2-carboxylate; and ２ to obtain methyl-5-methyltetrahydrofuran-2-carboxylate; and a transesterified hydrogenated furoate production step of reacting methyl-5-methyltetrahydrofuran-2-carboxylate with an alcohol to obtain a fragrance containing a compound represented by the following formula (2): In formula (2), R ２ represents a linear, branched or cyclic alkyl group having 3 to 12 carbon atoms.

10. In formula (2), R ２ The method for producing a fragrance according to claim 9, wherein represents a linear or branched alkyl group having 3 to 12 carbon atoms.

11. A compound represented by the following formula (2-1):

12. A compound represented by the following formula (2-2):