Isobutyric acid ester compounds having an alkenoyloxy group at the α-position, fragrance compositions, and use as fragrances

Abstract

The present invention provides a perfume composition containing a compound represented by the formula (1) as an active ingredient. (In formula (1), R1 represents a C2-4 linear or branched olefinic unsaturated hydrocarbon group, and R2 represents a C1-6 linear, branched, or cyclic alkyl group.)

Description

[Technical Field]

[0001] This invention relates to isobutyric acid ester compounds having an alkenoyloxy group at the α-position, fragrance compositions, and their use as fragrances. [Background technology]

[0002] Some isobutyrate compounds are used as fragrances. For example, Non-Patent Document 1 states that methyl isobutyrate has a sweet apricot-like fruit aroma, propyl isobutyrate has a heavy pineapple-like aroma, butyl isobutyrate has a fresh apple and banana-like fruit aroma, and isoamyl isobutyrate has a sweet apricot and pineapple-like aroma. Furthermore, Patent Document 1 discloses that isobutyric acid ester compounds having a butyryloxy group or a pivaloyloxy group at the α-position have a mint-like or damascone-like aroma and can be used as raw materials for fragrances and blended fragrances.

[0003] On the other hand, Patent Documents 2 and 3 disclose that isobutyric acid esters having an acryloyloxy group or a methacryloyloxy group at the α-position can be used as raw materials for resists, Patent Document 4 discloses that these can be used as raw materials for molding materials such as optical lenses, and Patent Document 5 discloses that they can be used as raw materials for pressure-sensitive adhesives. However, there is no description of their fragrance characteristics, fragrance compositions containing them, or methods for using them as fragrances. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2020 / 004464 [Patent Document 2] Japanese Patent Application Publication No. 11-024274 [Patent Document 3] Japanese Patent Publication No. 2017-120403 [Patent Document 4] International Publication No. 2011 / 051032 [Patent Document 5] International Publication No. 2014 / 099300 [Non-patent literature]

[0005] [Non-Patent Document 1] "Synthetic Fragrances: Chemistry and Product Knowledge, Revised and Expanded Edition," Chemical Daily Co., Ltd., 2016, pp. 580-582. [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] As mentioned above, isobutyrate ester compounds include those used as fragrances. Fragrances are used in a variety of fields, including fragrance products, detergents, general merchandise, pharmaceuticals, and food products. However, to enhance the value of these products, there is a demand for fragrances with novel scents. Therefore, the present invention aims to provide a fragrance composition containing an isobutyric acid ester compound as an active ingredient, which is useful as a fragrance because it has a complex fragrance of floral and other aromas, and which, in addition to the aforementioned fragrance, is given strength and diffusivity of the fragrance. Furthermore, the present invention aims to provide an isobutyric acid ester compound having a complex fragrance of floral and other aromas, and its use as a fragrance. [Means for solving the problem]

[0007] The inventors synthesized various compounds and diligently studied their aromas, and found that a fragrance composition containing an isobutyric acid ester compound having an alkenoyloxy group at a specific α-position as an active ingredient solves the aforementioned problem. Furthermore, they found that the aforementioned problem can also be solved by using an isobutyric acid ester compound having an alkenoyloxy group at a specific α-position and using it as a fragrance. In other words, the present invention is as follows:

[0008] <1>A perfume composition containing, as an active ingredient, a compound represented by the following formula (1). [Chemical formula] (In formula (1), R 1 , 1 , , 1 , 2 , , 1 , 1 , 1 , 1 , 1 , 2 , , 2 , 2 , 2 , 2 , , 2 , 2 , 2 , 2 is a linear or branched olefinic unsaturated hydrocarbon group having 2 to 4 carbon atoms, and R 2 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.) <2>In formula (1), the perfume composition according to <1> above, wherein R 1 is a linear or branched olefinic unsaturated hydrocarbon group having 3 to 4 carbon atoms. <3>In formula (1), the perfume composition according to <1> or <2> above, wherein R 1 is an isopropenyl group. <4>In formula (1), the perfume composition according to any one of <1> to <3> above, wherein R 2 is a branched alkyl group having 3 to 4 carbon atoms. <5>In formula (1), the perfume composition according to any one of <1> to <4> above, wherein R 2 is an isopropyl group or a secondary butyl group. <6>In formula (1), the perfume composition according to any one of <1> to <5> above, wherein R 2 is an isopropyl group. <7>In formula (1), R 1 is an isopropenyl group and R 2 is an isopropyl group, R 1 is an isopropenyl group and R<00​​​​​​​​​​​​​​​​​​​​The above is an isopropyl group. <1> The fragrance composition described above. <8> Use of the compound represented by the following formula (1) as a fragrance. [ka] (In formula (1), R 1 R is a linear or branched olefinic unsaturated hydrocarbon group having 2 to 4 carbon atoms, 2 (It is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms.) <9> A compound represented by the following formula (2). [ka] (In formula (2), R 3 R is a linear or branched olefinic unsaturated hydrocarbon group having 3 to 4 carbon atoms, 4 R is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. However, R 3 (Excluding the isopropenyl group.) <10> In formula (2), R 4 The above is a branched alkyl group having 3 to 4 carbon atoms. <9> The compounds described above. <11> In formula (2), R 4 The above, wherein is an isopropyl group or a secondary butyl group. <9> or <10> The compounds described above. <12> In formula (2), R 4 The above is an isopropyl group. <9> ~ <11> A compound listed in any one of the following. [Effects of the Invention]

[0009] According to the present invention, a fragrance composition can be provided that contains an isobutyric acid ester compound as an active ingredient, which is useful as a fragrance because it has a complex fragrance of floral and other aromas, and which, in addition to the aforementioned fragrance, is given strength and diffusivity of the fragrance. Furthermore, an isobutyric acid ester compound having a complex fragrance of floral and other aromas, and its use as a fragrance can also be provided. [Modes for carrying out the invention]

[0010] [Fragrance composition] The fragrance composition of the present invention contains a compound represented by the following formula (1) as an active ingredient. The present invention will be described in detail below. <Compound represented by formula (1)> The compound represented by the following formula (1) is contained as an active ingredient in the fragrance composition of the present invention. [ka] (In formula (1), R 1 R is a linear or branched olefinic unsaturated hydrocarbon group having 2 to 4 carbon atoms, 2 (It is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms.)

[0011] The compound represented by formula (1) above has a complex fragrance of floral and other aromas, and in addition to the aforementioned fragrance, it can impart fragrance strength and diffusivity to the fragrance composition. In particular, the compound represented by formula (1) above has a floral fragrance, and in addition to R 1 or R 2 Depending on the differences, it can simultaneously exhibit aromas such as green, rose, herbal, woody, balsamic, and fruity.

[0012] In formula (1), R 1 R is a linear or branched olefinic unsaturated hydrocarbon group having 2 to 4 carbon atoms, preferably a linear or branched olefinic unsaturated hydrocarbon group having 3 to 4 carbon atoms, and more preferably a linear or branched olefinic unsaturated hydrocarbon group having 3 carbon atoms. 1 It may have an internal carbon-carbon double bond, a terminal carbon-carbon double bond, or both. R 1 If has one or more carbon-carbon double bonds, the compound represented by formula (1) includes one or any proportion of the resulting stereoisomers.

[0013] R 1 Specific examples include vinyl group, 1-propenyl group, 2-propenyl group (allyl group), isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-methyl-1-propenyl group, and 2-methyl-1-propenyl group. Preferably, it is 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 1-methyl-1-propenyl group, or 2-methyl-1-propenyl group. More preferably, it is 1-propenyl group, isopropenyl group, 1-butenyl group, 1-methyl-1-propenyl group, or 2-methyl-1-propenyl group. Even more preferably, it isopropenyl group.

[0014] The compound represented by the above formula (1) is Preferably, R 1 This is an isopropenyl group. Preferably, R 1 This is a 1-propenyl group. Preferably, R 1 This is a 1-butenyl group. Preferably, R 1 This is a 1-methyl-1-propenyl group. Preferably, R 1 This is the 2-methyl-1-propenyl group.

[0015] In formula (1), R 2 The alkyl group is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, preferably a linear or branched alkyl group having 3 to 4 carbon atoms. R 2 If the carbon atom has one or more chiral carbon atoms, the compound represented by formula (1) includes one or any proportion of the resulting optical isomers.

[0016] R 2Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group (2-methylpropyl group), secondary butyl group (1-methylpropyl group), tertiary butyl group, n-pentyl group, 1-methylbutyl group (2-pentyl group), 2-methylbutyl group, 3-methylbutyl group, neopentyl group (2,2-dimethylpropyl group), 2-methylbutan-2-yl group, 1-ethylpropyl group (3-pentyl group), 3-methylbutan-2-yl group, n-hexyl group, 1-methylpentyl group (2-hexyl group), 2-methylpentyl group, 3- Examples include methylpentyl group, 4-methylpentyl group, 2-methylpentan-2-yl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 3-methylpentan-2-yl group, 2,3-dimethylbutyl group, 4-methylpentan-2-yl group, 3-hexyl group, 2-ethylbutyl group, 2,3-dimethylbutan-2-yl group, 3,3-dimethylbutan-2-yl group, 4-methylpentan-3-yl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group, preferably isopropyl group or secondary butyl group, and more preferably isopropyl group.

[0017] The compound represented by the above formula (1) is Preferably, R 2 This is an isopropyl group. Preferably, R 2 This is a secondary butyl group.

[0018] In equation (1), R 1 and R 2 As for combinations, R 1 R is a linear or branched olefinic unsaturated hydrocarbon group having 3 to 4 carbon atoms, 2 A combination in which is a linear or branched alkyl group having 3 to 4 carbon atoms is preferred, R 1 is a linear or branched olefinic unsaturated hydrocarbon group having 3 carbon atoms, and R 2 A combination in which is a linear or branched alkyl group having 3 to 4 carbon atoms is more preferable, 1is a linear or branched olefinic unsaturated hydrocarbon group having 3 carbon atoms, and R 2 A combination in which is a branched alkyl group having 3 to 4 carbon atoms is even more preferred, 1 is a linear or branched olefinic unsaturated hydrocarbon group having 3 carbon atoms, and R 2 A combination in which is a branched alkyl group having 3 carbon atoms is even more preferable. Specifically, R 1 is one selected from the group consisting of a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 1-methyl-1-propenyl group, and a 2-methyl-1-propenyl group, R 2 A combination in which is selected from the group consisting of isopropyl groups and secondary butyl groups is more preferable. The compound represented by the above formula (1) is Particularly preferred, R 1 is an isopropenyl group, and R 2 This is an isopropyl group. Particularly preferred, R 1 is an isopropenyl group, and R 2 This is a secondary butyl group. Particularly preferred, R 1 is a 1-propenyl group, and R 2 This is an isopropyl group. Particularly preferred, R 1 is a 1-propenyl group, and R 2 This is a secondary butyl group. Particularly preferred, R 1 is a 1-butenyl group, and R 2 This is an isopropyl group. Particularly preferred, R 1 is a 1-methyl-1-propenyl group, and R 2 This is an isopropyl group. Particularly preferred, R 1 is a 2-methyl-1-propenyl group, and R 2 This is an isopropyl group. That is, in equation (1), R 1 is an isopropenyl group and R 2 is an isopropyl group, R 1 is an isopropenyl group and R2 The secondary butyl group, R 1 is a 1-propenyl group and R 2 is an isopropyl group, R 1 is a 1-propenyl group and R 2 The secondary butyl group, R 1 is a 1-butenyl group and R 2 is an isopropyl group, R 1 is a 1-methyl-1-propenyl group and R 2 is an isopropyl group, or R 1 is a 2-methyl-1-propenyl group and R 2 Compounds having an isopropyl group are particularly preferably included as active ingredients in the fragrance composition of the present invention.

[0019] In the present invention, examples of compounds represented by formula (1) include compounds represented by any of the following formulas (1-1) to (1-96). Among these, preferred compounds are those represented by any of the following formulas (1-12), (1-16), (1-28), (1-32), (1-36), (1-60), and (1-84).

[0020] [ka]

[0021] [ka]

[0022] [ka]

[0023] [ka]

[0024] [ka]

[0025] [ka]

[0026] [ka]

[0027] [ka]

[0028] [ka]

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] Formula (1-9), Formula (1-10), Formula (1-11), Formula (1-12), Formula (1-13), Formula (1-14), Formula (1-15), Formula (1-16), Formula (1-33), Formula (1-34), Formula ( 1-35), formula (1-36), formula (1-37), formula (1-38), formula (1-39), formula (1-40), formula (1-41), formula (1-42), formula (1-43), formula (1-44), formula (1) In formulas (1-45), (1-46), (1-47), (1-48), (1-57), (1-58), (1-59), (1-60), (1-61), (1-62), (1-63), and (1-64), the carbon-carbon double bond represented by the intersecting double line indicates both the trans (E) and cis (Z) stereoisomers resulting from that double bond.

[0033] The compound represented by formula (1) has a complex fragrance of floral and other aromas. Therefore, by incorporating the compound represented by formula (1) as an active ingredient in a fragrance composition, a complex fragrance of floral and other aromas can be imparted. Furthermore, the compound represented by formula (1) can impart strength and diffusivity of the fragrance composition. In particular, the compound represented by formula (1) above has a floral aroma, and in addition, R 1 or R 2 Because the differences in these compounds simultaneously produce aromas such as green, rose, herbal, woody, balsamic, and fruity notes, incorporating the compound represented by formula (1) as an active ingredient in a fragrance composition can simultaneously impart floral aromas along with green, rose, herbal, woody, balsamic, and fruity notes. Furthermore, the compound represented by formula (1) can impart strength and diffusivity of the fragrance composition. A fragrance composition containing the compound represented by formula (1) as an active ingredient is a fragrance composition that, in addition to the aforementioned fragrance, is endowed with increased fragrance strength and diffusivity. In a fragrance composition, the term "active ingredient" refers to an ingredient that alters the fragrance of the fragrance composition, and more specifically, an ingredient that changes the fragrance of the fragrance composition to a desirable scent profile, and an ingredient that has the property of improving the fragrance of the fragrance composition.

[0034] The content of the compound represented by formula (1) in the fragrance composition may be appropriately changed depending on the type of compound and the type and strength of the desired fragrance, but the content of the compound represented by formula (1) in the fragrance composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more. Furthermore, it is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less.

[0035] <Composition and other components of the fragrance composition> The fragrance composition of the present invention contains a compound represented by formula (1) as an active ingredient. However, it is not particularly limited as long as it contains at least one compound represented by formula (1), and may contain two or more compounds represented by formula (1). The fragrance composition of the present invention only needs to contain the compound represented by formula (1) as an active ingredient, and is not particularly limited to other components, but it is preferable to further contain fragrances other than the compound represented by formula (1). Furthermore, "fragrance composition" refers to a composition that imparts fragrance when added to various cosmetics, pharmaceuticals, foods, beverages, etc., or a composition that is used as a perfume or the like by itself. In addition to the compound represented by formula (1) and fragrances other than the compound represented by formula (1), it may also contain additives such as solvents as needed.

[0036] Other components in the fragrance composition of the present invention, other than the compound represented by formula (1), include fragrances other than the compound represented by formula (1), surfactants, solvents, antioxidants, and colorants. Preferably, at least one is selected from the group consisting of fragrances other than the compound represented by formula (1), surfactants, solvents, antioxidants, and colorants, and more preferably, at least one is selected from the group consisting of fragrances other than the compound represented by formula (1) and solvents. By including fragrances other than the compound represented by formula (1), the fragrance can be adjusted to suit the target product. Furthermore, by including a solvent, it becomes easier to dissolve and impregnate the target product, allowing for adjustment of the fragrance intensity and duration.

[0037] Aside from the compound represented by formula (1), there are no particular restrictions on the fragrances as long as they are conventionally known fragrance components. A wide range of fragrances can be used, for example, one or more of the following can be selected and used in any mixing ratio.

[0038] Other fragrances besides the compound represented by formula (1) include hydrocarbons, alcohols, phenols, esters, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, natural essential oils, and natural extracts.

[0039] Examples of hydrocarbons include limonene, α-pinene, β-pinene, terpinene, cedrene, longifolene, and valencene. Alcohols include linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenoyl, ethyllinalool, farnesol, nerolidol, cis-3-hexenol, cedrol, menthol, borneol, β-phenylethyl alcohol, benzyl alcohol, phenylhexanol, 2,2,6-trimethylcyclohexyl-3-hexanol, 1-(2-t-butylcyclohexyloxy)-2-butanol, 4-isopropyl cyclohexyl Examples include hexahexanemethanol, 4-t-butylcyclohexanol, 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, isocamphyllcyclohexanol, 3,7-dimethyl-7-methoxyoctan-2-ol, etc. Examples of phenols include eugenol, thymol, and vanillin. Esters include linalyl formate, citronellyl formate, geranyl formate, n-hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, terpinyl acetate, nopyl acetate, bornyl acetate, isobornyl acetate, ot-butylcyclohexyl acetate, pt-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styraryl acetate, cinnamyl acetate, dimethylbenzylcarbinyl acetate, 3-pentyltetrahydropyran-4-yl acetate, citronellyl propionate, tricyclodecenyl propionate Examples include nates, allylcyclohexylpropionate, ethyl 2-cyclohexylpropionate, benzylpropionate, citronellyl butyrate, dimethylbenzylcarbyl n-butyrate, tricyclodecenyl isobutyrate, methyl 2-nonenoate, methyl benzoate, benzyl benzoate, methyl cinnamate, methyl salicylate, n-hexyl salicylate, cis-3-hexenyl salicylate, geranyl tigrate, cis-3-hexenyl tigrate, methyl jasmonate, methyl dihydrojasmonate, methyl-2,4-dihydroxy-3,6-dimethylbenzoate, ethylmethylphenylglycidate, methyl anthranylate, and frutetes.

[0040] Examples of aldehydes include n-octanal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecenal, citronellal, citral, hydroxycitronellal, dimethyltetrahydrobenzaldehyde, 4(3)-(4-hydroxy-4-methylpentyl)-3-cyclohexen-1-carbaldehyde, 2-cyclohexylpropanal, pt-butyl-α-methylhydrocinnamicaldehyde, p-isopropyl-α-methylhydrocinnamicaldehyde, p-ethyl-α,α-dimethylhydrocinnamicaldehyde, α-amylcinnamicaldehyde, α-hexylcinnamicaldehyde, piperonal, and α-methyl-3,4-methylenedioxyhydrocinnamicaldehyde. Examples of ketones include 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, citric acid, nootkatone, benzylacetone, anisylacetone, methyl β-naphthyl ketone, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, maltol, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, muscone, cibetone, cyclopentadecanone, and cyclohexadecenone. Examples of acetals and ketals include acetaldehyde ethylphenylpropyl acetal, citral diethyl acetal, phenylacetaldehyde glycerin acetal, and ethyl acetacetate ethylene glycol ketal. Examples of ethers include anethole, β-naphthylmethyl ether, β-naphthylethyl ether, limonene oxide, rose oxide, 1,8-cineole, racemic mixtures, or optically active dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan. Examples of nitriles include citronellyl nitrile. Examples of lactones include γ-nonalactone, γ-undecalactone, σ-decalactone, γ-jasmolactone, coumarin, cyclopentadecanolide, cyclohexadecanolide, ambrettelide, ethylenebrasilate, and 11-oxahexadecanolide. Examples of natural essential oils and extracts include orange, lemon, bergamot, mandarin, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, geranium, jasmine, ylang-ylang, anise, clove, ginger, nutmeg, cardamom, cedar, cypress, sandalwood, vetiver, patchouli, and labdanum.

[0041] Other examples of solvents include dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, and triethyl citrate. Examples of surfactants include polyoxyethylene lauryl sulfate ether.

[0042] A fragrance composition containing the compound represented by formula (1) as an active ingredient can be used as a fragrance component in various products. Examples of products that can use the fragrance composition include: fragrance products such as perfumes and colognes; shampoos, conditioners, hair tonics, hair creams, mousses, gels, pomades, sprays, and other hair cosmetics; skin cosmetics such as lotions, serums, creams, emulsions, masks, foundations, face powders, lipsticks, and various makeup products; dishwashing detergents, laundry detergents, softeners, disinfectants, deodorizers, room fresheners, furniture care products, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, sterilizers, repellents, and other various health and hygiene detergents; quasi-drugs such as toothpaste, mouthwash, bath additives, antiperspirants, and perming solutions; general merchandise such as toilet paper and tissues; pharmaceuticals; and food products.

[0043] The amount of fragrance composition in the above product is not particularly limited, and the amount of fragrance composition can be selected according to the type, properties, and sensory effects of the product to be scented. For example, the amount of fragrance composition in the product is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.001% by mass or more. It is also preferably 80% by mass or less, even more preferably 60% by mass or less, and even more preferably 40% by mass or less. Furthermore, when using the fragrance composition as an aroma oil, perfume, etc., the amount of the fragrance composition in the product may be 80% by mass or more, or 100% by mass.

[0044] [Use of the compound represented by formula (1) as a fragrance] The compound represented by the following formula (1) can be used as a fragrance. The present invention also provides the use of the compound represented by formula (1) as a fragrance. [Chemical formula] (In formula (1), R 1 is a linear or branched olefinic unsaturated hydrocarbon group having 2 to 4 carbon atoms, and R 2 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.)

[0045] Since the compound represented by the above formula (1) has a complex fragrance of a floral fragrance and other fragrances, it can be used as a fragrance. In particular, the compound represented by the above formula (1) has a floral fragrance, and in addition, due to the difference in R 1 or R 2 it also simultaneously exhibits fragrances such as green, rose, herbal, woody, balsamic, and fruity, so it can be used as a fragrance.

[0046] The compound represented by formula (1) that can be used as a fragrance is the same as the compound described in the <Compound represented by formula (1)> section of the above [Fragrance composition], and the preferred structures are also the same. Specifically, it is as follows.

[0047] In formula (1), R 1 is a linear or branched olefinic unsaturated hydrocarbon group having 2 to 4 carbon atoms, preferably a linear or branched olefinic unsaturated hydrocarbon group having 3 to 4 carbon atoms, and more preferably a linear or branched olefinic unsaturated hydrocarbon group having 3 carbon atoms. R 1 may have an internal carbon-carbon double bond, may have a terminal carbon-carbon double bond, or may have both. R 1 When R has one or more carbon-carbon double bonds, the compound represented by formula (1) includes any one of the stereoisomers generated thereby or a mixture in an arbitrary ratio.

[0048] R 1 Specific examples of 1 include a vinyl group, 1-propenyl group, 2-propenyl group (allyl group), isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-methylene-propyl group, 2-methyl-1-propenyl group, and 2-methylene-propyl group. Preferably, it is a 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 1-methyl-1-propenyl group or 2-methyl-1-propenyl group, more preferably a 1-propenyl group, isopropenyl group, 1-butenyl group, 1-methyl-1-propenyl group or 2-methyl-1-propenyl group, and still more preferably an isopropenyl group.

[0049] The compound represented by the above formula (1) Preferably, R 1 is an isopropenyl group. Preferably, R 1 is a 1-propenyl group. Preferably, R 1 is a 1-butenyl group. Preferably, R 1 is a 1-methyl-1-propenyl group. Preferably, R 1 is a 2-methyl-1-propenyl group.

[0050] In formula (1), R 2 is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, preferably a linear or branched alkyl group having 3 to 4 carbon atoms. R 2 When R has one or more asymmetric carbons, the compound represented by formula (1) includes any one of the optical isomers generated thereby or a mixture in any ratio.

[0051] R 2Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group (2-methylpropyl group), secondary butyl group (1-methylpropyl group), tertiary butyl group, n-pentyl group, 1-methylbutyl group (2-pentyl group), 2-methylbutyl group, 3-methylbutyl group, neopentyl group (2,2-dimethylpropyl group), 2-methylbutan-2-yl group, 1-ethylpropyl group (3-pentyl group), 3-methylbutan-2-yl group, n-hexyl group, 1-methylpentyl group (2-hexyl group), 2-methylpentyl group, 3- Examples include methylpentyl group, 4-methylpentyl group, 2-methylpentan-2-yl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 3-methylpentan-2-yl group, 2,3-dimethylbutyl group, 4-methylpentan-2-yl group, 3-hexyl group, 2-ethylbutyl group, 2,3-dimethylbutan-2-yl group, 3,3-dimethylbutan-2-yl group, 4-methylpentan-3-yl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group, preferably isopropyl group or secondary butyl group, and more preferably isopropyl group.

[0052] The compound represented by the above formula (1) is Preferably, R 2 This is an isopropyl group. Preferably, R 2 This is a secondary butyl group.

[0053] In equation (1), R 1 and R 2 As for combinations, R 1 R is a linear or branched olefinic unsaturated hydrocarbon group having 3 to 4 carbon atoms, 2 A combination in which is a linear or branched alkyl group having 3 to 4 carbon atoms is preferred, R 1 is a linear or branched olefinic unsaturated hydrocarbon group having 3 carbon atoms, and R 2 A combination in which is a linear or branched alkyl group having 3 to 4 carbon atoms is more preferable, 1is a linear or branched olefinic unsaturated hydrocarbon group having 3 carbon atoms, and R 2 A combination in which is a branched alkyl group having 3 to 4 carbon atoms is even more preferred, 1 is a linear or branched olefinic unsaturated hydrocarbon group having 3 carbon atoms, and R 2 A combination in which is a branched alkyl group having 3 carbon atoms is even more preferable. Specifically, R 1 is one selected from the group consisting of a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 1-methyl-1-propenyl group, and a 2-methyl-1-propenyl group, R 2 A combination in which is selected from the group consisting of isopropyl groups and secondary butyl groups is more preferable. The compound represented by the above formula (1) is Particularly preferred, R 1 is an isopropenyl group, and R 2 This is an isopropyl group. Particularly preferred, R 1 is an isopropenyl group, and R 2 This is a secondary butyl group. Particularly preferred, R 1 is a 1-propenyl group, and R 2 This is an isopropyl group. Particularly preferred, R 1 is a 1-propenyl group, and R 2 This is a secondary butyl group. Particularly preferred, R 1 is a 1-butenyl group, and R 2 This is an isopropyl group. Particularly preferred, R 1 is a 1-methyl-1-propenyl group, and R 2 This is an isopropyl group. Particularly preferred, R 1 is a 2-methyl-1-propenyl group, and R 2 This is an isopropyl group. That is, in equation (1), R 1 is an isopropenyl group and R 2 is an isopropyl group, R 1 is an isopropenyl group and R2 The secondary butyl group, R 1 is a 1-propenyl group and R 2 is an isopropyl group, R 1 is a 1-propenyl group and R 2 The secondary butyl group, R 1 is a 1-butenyl group and R 2 is an isopropyl group, R 1 is a 1-methyl-1-propenyl group and R 2 is an isopropyl group, or R 1 is a 2-methyl-1-propenyl group and R 2 Compounds in which the group is an isopropyl group are particularly preferred as fragrances.

[0054] [Compound represented by formula (2)] The compound of the present invention is represented by the following formula (2). [ka] (In formula (2), R 3 R is a linear or branched olefinic unsaturated hydrocarbon group having 3 to 4 carbon atoms, 4 R is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. However, R 3 (Excluding the isopropenyl group.)

[0055] The compound represented by formula (2) above is useful as a fragrance because it has a complex aroma of floral and other fragrances. In particular, the compound represented by formula (2) above has a floral aroma, and in addition to that R 3 or R 4 Because it exhibits various aromas such as green, rose, herbal, woody, balsamic, and fruity depending on the differences in these characteristics, it is useful as a fragrance ingredient.

[0056] In formula (2), R 3 R is a linear or branched olefinic unsaturated hydrocarbon group having 3 to 4 carbon atoms, excluding the isopropenyl group, and more preferably a linear or branched olefinic unsaturated hydrocarbon group having 3 carbon atoms. 3It may have an internal carbon-carbon double bond, a terminal carbon-carbon double bond, or both. R 3 If has one or more carbon-carbon double bonds, the compound represented by formula (2) includes one or any proportion of the resulting stereoisomers.

[0057] R 3 Specific examples include 1-propenyl group, 2-propenyl group (allyl group), 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-methylidene-propyl group, 2-methyl-1-propenyl group, and 2-methylidene-propyl group, with 1-propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, or 2-methyl-1-propenyl group being preferred.

[0058] The compound represented by the above formula (2) is Preferably, R 3 This is a 1-propenyl group. Preferably, R 3 This is a 1-butenyl group. Preferably, R 3 This is a 1-methyl-1-propenyl group. Preferably, R 3 This is the 2-methyl-1-propenyl group.

[0059] In formula (2), R 4 The alkyl group is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, preferably a linear or branched alkyl group having 3 to 4 carbon atoms. R 4 If the carbon atom has one or more chiral carbon atoms, the compound represented by formula (2) includes one or any proportion of the resulting optical isomers.

[0060] R 4Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group (2-methylpropyl group), secondary butyl group (1-methylpropyl group), tertiary butyl group, n-pentyl group, 1-methylbutyl group (2-pentyl group), 2-methylbutyl group, 3-methylbutyl group, neopentyl group (2,2-dimethylpropyl group), 2-methylbutan-2-yl group, 1-ethylpropyl group (3-pentyl group), 3-methylbutan-2-yl group, n-hexyl group, 1-methylpentyl group (2-hexyl group), 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl Examples of groups include the 2-methylpentan-2-yl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 3-methylpentan-2-yl group, 2,3-dimethylbutyl group, 4-methylpentan-2-yl group, 3-hexyl group, 2-ethylbutyl group, 2,3-dimethylbutan-2-yl group, 3,3-dimethylbutan-2-yl group, 4-methylpentan-3-yl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group, preferably isopropyl group, secondary butyl group or isobutyl group, more preferably isopropyl group or secondary butyl group, and even more preferably isopropyl group.

[0061] The compound represented by the above formula (2) is Preferably, R 4 This is an isopropyl group. Preferably, R 4 This is a secondary butyl group.

[0062] In equation (2), R 3 and R 4 As for combinations, R 3 R is a linear or branched olefinic unsaturated hydrocarbon group having 3 to 4 carbon atoms, 4 A combination in which is a linear or branched alkyl group having 3 to 4 carbon atoms is preferred, R 3 is a linear or branched olefinic unsaturated hydrocarbon group having 3 carbon atoms, and R 4 A combination in which is a linear or branched alkyl group having 3 to 4 carbon atoms is more preferable,3 is a linear or branched olefinic unsaturated hydrocarbon group having 3 carbon atoms, and R 4 A combination in which is a branched alkyl group having 3 to 4 carbon atoms is even more preferred, 3 is a linear or branched olefinic unsaturated hydrocarbon group having 3 carbon atoms, and R 4 A combination in which is a branched alkyl group having 3 carbon atoms is even more preferable. Specifically, R 3 is one selected from the group consisting of a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 1-methyl-1-propenyl group, and a 2-methyl-1-propenyl group, R 4 A combination in which is selected from the group consisting of isopropyl groups and secondary butyl groups is more preferable. The compound represented by the above formula (2) is Particularly preferred, R 3 is a 1-propenyl group, and R 4 This is an isopropyl group. Particularly preferred, R 3 is a 1-propenyl group, and R 4 This is a secondary butyl group. Particularly preferred, R 3 is a 1-butenyl group, and R 4 This is an isopropyl group. Particularly preferred, R 3 is a 1-methyl-1-propenyl group, and R 4 This is an isopropyl group. Particularly preferred, R 3 is a 2-methyl-1-propenyl group, and R 4 This is an isopropyl group.

[0063] In the present invention, examples of compounds represented by formula (2) include compounds represented by any of the following formulas (2-1) to (2-80). Among these, preferred compounds are those represented by any of the following formulas (2-4), (2-8), (2-20), (2-44), and (2-68).

[0064] [ka]

[0065]

change

[0066]

change

[0067]

change

[0068]

change

[0069]

change

[0070]

change

[0071]

change

[0072]

change

[0073]

change

[0074] Formula (2-1), Formula (2-2), Formula (2-3), Formula (2-4), Formula (2-6), Formula (2-7), Formula (2-8), Formula (2-17), Formula (2-18), Formula (2-19), Formula (2- 20), Formula (2-21), Formula (2-22), Formula (2-23), Formula (2-24), Formula (2-25), Formula (2-26), Formula (2-27), Formula (2-28), Formula (2-29), Formula In equations (2-30), (2-31), (2-32), (2-41), (2-42), (2-43), (2-44), (2-45), (2-46), (2-47), and (2-48), the carbon-carbon double bond represented by the intersecting double line indicates both the trans (E) and cis (Z) stereoisomers resulting from that double bond.

[0075] The compound represented by formula (2) is useful as a fragrance because it has a complex aroma of floral and other scents. In particular, the compound represented by formula (2) has a floral aroma, and in addition, R 3 or R 4 Because it exhibits various aromas such as green, rose, herbal, woody, balsamic, and fruity depending on the differences in these characteristics, it is useful as a fragrance ingredient.

[0076] The compound represented by formula (2) can be used as an aroma component in various products. Products in which the compound represented by formula (2) can be used as a fragrance component include, for example, fragrance products such as perfumes and colognes; shampoos, conditioners, hair tonics, hair creams, mousses, gels, pomades, sprays and other hair cosmetics; skin cosmetics such as lotions, serums, creams, emulsions, masks, foundations, face powders, lipsticks and various makeup products; dishwashing detergents, laundry detergents, softeners, disinfectants, deodorizers, room fresheners, furniture care products, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, sterilizers, repellents and other various health and hygiene detergents; quasi-drugs such as toothpaste, mouthwash, bath additives, antiperspirants, and perming solutions; general merchandise such as toilet paper and tissues; pharmaceuticals; and food products.

[0077] The amount of the compound represented by formula (2) in the above product is not particularly limited, and the amount of the compound represented by formula (2) can be selected according to the type, properties, and sensory effects of the product to be flavored. For example, the amount of the compound represented by formula (2) in the product is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.001% by mass or more. It is also preferably 80% by mass or less, even more preferably 60% by mass or less, and even more preferably 40% by mass or less. Furthermore, when the compound represented by formula (2) is used as an aroma oil, perfume, etc., the amount of the compound represented by formula (2) in the product may be 80% by mass or more, or 100% by mass.

[0078] <Fragrance composition containing the compound represented by formula (2) as an active ingredient> The compound represented by formula (2) below in the present invention is also useful as an active ingredient in fragrance compositions. A fragrance composition containing the compound represented by formula (2) as an active ingredient will be described below. [ka] (In formula (2), R 3 R is a linear or branched olefinic unsaturated hydrocarbon group having 3 to 4 carbon atoms, 4 R is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. However, R 3 (Excluding the isopropenyl group.)

[0079] The compound represented by formula (2) has a complex fragrance of floral and other aromas. Therefore, by incorporating the compound represented by formula (2) as an active ingredient in a fragrance composition, a complex fragrance of floral and other aromas can be imparted. Furthermore, the compound represented by formula (2) can impart strength and diffusivity of the fragrance composition. In particular, the compound represented by formula (2) above has a floral aroma, and in addition, R 3 or R4 Because the differences in these compounds simultaneously produce aromas such as green, rose, herbal, woody, balsamic, and fruity notes, incorporating the compound represented by formula (2) as an active ingredient in a fragrance composition can simultaneously impart floral aromas along with green, rose, herbal, woody, balsamic, and fruity notes. Furthermore, the compound represented by formula (2) can impart strength and diffusivity of the fragrance composition. A fragrance composition containing the compound represented by formula (2) as an active ingredient is a fragrance composition that, in addition to the aforementioned fragrance, is also provided with increased fragrance strength and diffusivity. In a fragrance composition, the term "active ingredient" refers to an ingredient that alters the fragrance of the fragrance composition, and more specifically, an ingredient that changes the fragrance of the fragrance composition to a desirable scent profile, and an ingredient that has the property of improving the fragrance of the fragrance composition.

[0080] The compound represented by formula (2) used as an active ingredient in the fragrance composition is identical to the compound represented by formula (2) described above, and also has the same preferred structure.

[0081] The content of the compound represented by formula (2) in the fragrance composition may be appropriately changed depending on the type of compound and the type and strength of the desired fragrance, but the content of the compound represented by formula (2) in the fragrance composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more. Furthermore, it is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less.

[0082] (Composition of the fragrance composition and other components) A fragrance composition containing a compound represented by formula (2) as an active ingredient is not particularly limited as long as it contains at least one compound represented by formula (2), and may contain two or more compounds represented by formula (2). A fragrance composition containing the compound represented by formula (2) as an active ingredient is acceptable as long as it contains the compound represented by formula (2) as an active ingredient, and is not particularly limited to other components, but it is preferable to further contain fragrances other than the compound represented by formula (2). Furthermore, "fragrance composition" refers to a composition that imparts fragrance when added to various cosmetics, pharmaceuticals, foods, beverages, etc., or a composition that is used as a perfume or the like by itself. In addition to the compound represented by formula (2) and fragrances other than the compound represented by formula (2), it may also contain additives such as solvents as needed.

[0083] Other components other than the compound represented by formula (2) contained in a fragrance composition containing the compound represented by formula (2) as an active ingredient include fragrances other than the compound represented by formula (2), surfactants, solvents, antioxidants, and colorants. Preferably, at least one is selected from the group consisting of fragrances other than the compound represented by formula (2), surfactants, solvents, antioxidants, and colorants, and more preferably, at least one is selected from the group consisting of fragrances other than the compound represented by formula (2) and solvents. By including fragrances other than the compound represented by formula (2), the fragrance can be adjusted to suit the target product. Furthermore, by including a solvent, it becomes easier to dissolve and impregnate the target product, allowing for adjustment of the fragrance intensity and duration.

[0084] Aside from the compound represented by formula (2), there are no particular restrictions on the fragrances as long as they are conventionally known fragrance components. A wide range of fragrances can be used, for example, one or more of the following can be selected and used in any mixing ratio.

[0085] Other fragrances besides the compound represented by formula (2) include hydrocarbons, alcohols, phenols, esters, aldehydes, ketones, acetals, ketals, ethers, nitriles, lactones, natural essential oils, and natural extracts.

[0086] Examples of hydrocarbons include limonene, α-pinene, β-pinene, terpinene, cedrene, longifolene, and valencene. Alcohols include linalool, citronellol, geraniol, nerol, terpineol, dihydromyrcenoyl, ethyllinalool, farnesol, nerolidol, cis-3-hexenol, cedrol, menthol, borneol, β-phenylethyl alcohol, benzyl alcohol, phenylhexanol, 2,2,6-trimethylcyclohexyl-3-hexanol, 1-(2-t-butylcyclohexyloxy)-2-butanol, 4-isopropyl cyclohexyl Examples include hexahexanemethanol, 4-t-butylcyclohexanol, 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, isocamphyllcyclohexanol, 3,7-dimethyl-7-methoxyoctan-2-ol, etc. Examples of phenols include eugenol, thymol, and vanillin. Esters include linalyl formate, citronellyl formate, geranyl formate, n-hexyl acetate, cis-3-hexenyl acetate, linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, terpinyl acetate, nopyl acetate, bornyl acetate, isobornyl acetate, ot-butylcyclohexyl acetate, pt-butylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, styraryl acetate, cinnamyl acetate, dimethylbenzylcarbinyl acetate, 3-pentyltetrahydropyran-4-yl acetate, citronellyl propionate, tricyclodecenyl propionate Examples include nates, allylcyclohexylpropionate, ethyl 2-cyclohexylpropionate, benzylpropionate, citronellyl butyrate, dimethylbenzylcarbyl n-butyrate, tricyclodecenyl isobutyrate, methyl 2-nonenoate, methyl benzoate, benzyl benzoate, methyl cinnamate, methyl salicylate, n-hexyl salicylate, cis-3-hexenyl salicylate, geranyl tigrate, cis-3-hexenyl tigrate, methyl jasmonate, methyl dihydrojasmonate, methyl-2,4-dihydroxy-3,6-dimethylbenzoate, ethylmethylphenylglycidate, methyl anthranylate, and frutetes.

[0087] Examples of aldehydes include n-octanal, n-decanal, n-dodecanal, 2-methylundecanal, 10-undecenal, citronellal, citral, hydroxycitronellal, dimethyltetrahydrobenzaldehyde, 4(3)-(4-hydroxy-4-methylpentyl)-3-cyclohexen-1-carbaldehyde, 2-cyclohexylpropanal, pt-butyl-α-methylhydrocinnamicaldehyde, p-isopropyl-α-methylhydrocinnamicaldehyde, p-ethyl-α,α-dimethylhydrocinnamicaldehyde, α-amylcinnamicaldehyde, α-hexylcinnamicaldehyde, piperonal, and α-methyl-3,4-methylenedioxyhydrocinnamicaldehyde. Examples of ketones include 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, citric acid, nootkatone, benzylacetone, anisylacetone, methyl β-naphthyl ketone, 2,5-dimethyl-4-hydroxy-3(2H)-furanone, maltol, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, muscone, cibetone, cyclopentadecanone, and cyclohexadecenone. Examples of acetals and ketals include acetaldehyde ethylphenylpropyl acetal, citral diethyl acetal, phenylacetaldehyde glycerin acetal, and ethyl acetacetate ethylene glycol ketal. Examples of ethers include anethole, β-naphthylmethyl ether, β-naphthylethyl ether, limonene oxide, rose oxide, 1,8-cineole, racemic mixtures, or optically active dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan. Examples of nitriles include citronellyl nitrile. Examples of lactones include γ-nonalactone, γ-undecalactone, σ-decalactone, γ-jasmolactone, coumarin, cyclopentadecanolide, cyclohexadecanolide, ambrettelide, ethylenebrasilate, and 11-oxahexadecanolide. Examples of natural essential oils and extracts include orange, lemon, bergamot, mandarin, peppermint, spearmint, lavender, chamomile, rosemary, eucalyptus, sage, basil, rose, geranium, jasmine, ylang-ylang, anise, clove, ginger, nutmeg, cardamom, cedar, cypress, sandalwood, vetiver, patchouli, and labdanum.

[0088] Other examples of solvents include dipropylene glycol, diethyl phthalate, ethylene glycol, propylene glycol, methyl myristate, and triethyl citrate. Examples of surfactants include polyoxyethylene lauryl sulfate ether.

[0089] A fragrance composition containing the compound represented by formula (2) as an active ingredient can be used as a fragrance component in various products. Examples of products that can use the fragrance composition include: fragrance products such as perfumes and colognes; shampoos, conditioners, hair tonics, hair creams, mousses, gels, pomades, sprays, and other hair cosmetics; skin cosmetics such as lotions, serums, creams, emulsions, masks, foundations, face powders, lipsticks, and various makeup products; dishwashing detergents, laundry detergents, softeners, disinfectants, deodorizers, room fresheners, furniture care products, glass cleaners, furniture cleaners, floor cleaners, disinfectants, insecticides, bleaches, sterilizers, repellents, and other various health and hygiene detergents; quasi-drugs such as toothpaste, mouthwash, bath additives, antiperspirants, and perming solutions; general merchandise such as toilet paper and tissues; pharmaceuticals; and food products.

[0090] The amount of fragrance composition in the above product is not particularly limited, and the amount of fragrance composition can be selected according to the type, properties, and sensory effects of the product to be scented. For example, the amount of fragrance composition in the product is preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more, and even more preferably 0.001% by mass or more. It is also preferably 80% by mass or less, even more preferably 60% by mass or less, and even more preferably 40% by mass or less. Furthermore, when using the fragrance composition as an aroma oil, perfume, etc., the amount of the fragrance composition in the product may be 80% by mass or more, or 100% by mass.

[0091] <Use of the compound represented by formula (2) as a fragrance> The compound represented by the following formula (2) can be used as a fragrance. [ka] (In formula (2), R 3 R is a linear or branched olefinic unsaturated hydrocarbon group having 3 to 4 carbon atoms, 4 R is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. However, R 3 (Excluding the isopropenyl group.)

[0092] The compound represented by formula (2) above has a complex fragrance of floral and other aromas and can therefore be used as a fragrance. In particular, the compound represented by formula (2) above has a floral fragrance, and in addition to that R 3 or R 4 Because the differences in these characteristics simultaneously exhibit aromas such as green, rose, herbal, woody, balsamic, and fruity notes, it can be used as a fragrance ingredient.

[0093] The compound represented by formula (2) that can be used as a fragrance is identical to the compound represented by formula (2) described above, and also has the same preferred structure.

[0094] [Method for producing the compound represented by formula (1) and method for producing the compound represented by formula (2)] There are no particular restrictions on the method for producing the compound represented by formula (1), and any method may be appropriately selected from conventionally known methods. Similarly, there are no particular restrictions on the method for producing the compound represented by formula (2), and any method may be appropriately selected from conventionally known methods. The following are preferred examples of methods for producing the compound represented by formula (1). The method for producing the compound represented by formula (2) is the same as the method for producing the compound represented by formula (1) shown below, but with respect to R in formulas (3) and (4). 1 to R 3 And, R 2 to R 4 Reinterpret it as follows.

[0095] For example, an isobutyric acid ester having an alkenoyloxy group at the α-position (a compound represented by formula (1)) can be produced by reacting an α-hydroxyisobutyric acid ester with an unsaturated acid anhydride. The reaction equation for this reaction is shown in formula (3) below. [ka] In formula (3), R 1 R is a linear or branched olefinic unsaturated hydrocarbon group having 2 to 4 carbon atoms. 2 This represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms.

[0096] Furthermore, an isobutyric acid ester having an alkenoyloxy group at the α-position (a compound represented by formula (1)) can be produced by reacting an α-hydroxyisobutyrate ester with an unsaturated carboxylic acid chloride in the presence of a catalyst. The reaction equation for this reaction is shown in formula (4) below. [ka] In formula (4), R 1 R is a linear or branched olefinic unsaturated hydrocarbon group having 2 to 4 carbon atoms. 2 This represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms.

[0097] The catalysts, reaction methods, reaction conditions, and reaction apparatus used in these reactions are not particularly limited and can be those of conventional known origin. Furthermore, known purification methods can be employed for purifying the resulting isobutyric acid ester having an alkenoyloxy group at the α-position (the compound represented by formula (1) or formula (2)). [Examples]

[0098] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0099] The reaction results were evaluated by the following formula. Reaction yield (%) = [(number of moles of the ester produced in the reaction solution) / (number of moles of the starting ester in the charged solution)] × 100%

[0100] [Analysis method · Separation method] <Gas chromatography analysis (GC analysis)> Apparatus: "GC-2010" (manufactured by Shimadzu Corporation, product name) Detector: FID Column: "DB-1" (J&W capillary column, product name) (0.25 mm φ × 30 m × 0.25 μm)

[0101] <NMR spectrum analysis> The identification of the ester was 1 performed by 1H-NMR measurement and 13 13C-NMR measurement. The measurement conditions are shown below. Apparatus: "ECA500" (manufactured by JEOL Ltd., product name) 1 [1H-NMR] Nucleus: 1 1H <000085{0}>Measurement frequency: 500 MHz Measurement sample: 5% CDCl3 solution 13 [13C-NMR] Nucleus: 13 13C Measurement frequency: 125 MHz Measurement sample: 5% CDCl3 solution

[0102] <Gas chromatography-mass spectrometry (GC-MS analysis)> <00{0}0859>The identification of the compound was also carried out by specifying the molecular weight by GC-MS measurement (chemical ionization method [CI+], high-resolution mass spectrometry [millimas]). The measurement conditions are shown below. GC apparatus: "Agilent 7890B" (manufactured by Agilent Technologies, product name) GC measurement conditions Column: "DB-1" (J&W capillary column, product name) (0.25 mm φ × 30 m × 0.25 μm) ​​MS device: "JMS-T200 GCx-plus" (manufactured by JEOL Ltd., product name) MS measurement conditions, chemical ionization method Ionization voltage: 200V Ion source: 200℃ Detector voltage: 2100V Reagent gas: Isobutane The exact mass values ​​of the fragments detected in a protonated state by chemical ionization, and the chemical formulas assigned to them, are listed.

[0103] <Isolation of the product by silica gel chromatography> The following materials were used for product isolation by silica gel chromatography in the examples. Filler: "Wako Gel C-200" (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product name) Developing solvent: ethyl acetate-hexane

[0104] [Example of raw material synthesis] <Synthesis Example 1: Synthesis of Isopropyl α-hydroxyisobutyrate> A 300 mL glass flask equipped with a distillation tube was packed with 88.7 g of methyl α-hydroxyisobutyrate (manufactured by Mitsubishi Gas Chemical Co., Ltd.), 106.1 g of isopropanol (manufactured by Fujifilm Wako Pure Chemical Corporation), and 0.21 g of sodium methoxide (manufactured by Fujifilm Wako Pure Chemical Corporation). The transesterification reaction was carried out for 48 hours under normal pressure (atmospheric pressure) by heating under reflux, while removing the methanol produced by the reaction from the system. As a result, isopropyl α-hydroxyisobutyrate was obtained in a reaction yield of 98.4% by the reaction of formula (5) below. After deactivating the catalyst by adding water to the reaction system, vacuum distillation was performed to obtain 77.7 g of isopropyl α-hydroxyisobutyrate (purity by GC analysis (hereinafter also referred to as GC purity): 99.6%) as a fraction at 40 mmHg and 65°C.

[0105] [ka]

[0106] <Synthesis Example 2: Synthesis of secondary butyl α-hydroxyisobutyrate> A 1 L glass flask equipped with a distillation tube was charged with 295 g of methyl α-hydroxyisobutyrate (manufactured by Mitsubishi Gas Chemical Company, Inc.), 203 g of secondary butanol (manufactured by Fujifilm Wako Pure Chemical Corporation), 2 g of sodium methoxide (manufactured by Fujifilm Wako Pure Chemical Corporation), and 15 mL of hexane. The mixture was heated to reflux under normal pressure (atmospheric pressure), and the transesterification reaction was carried out for 18 hours while extracting methanol produced by the reaction out of the system by azeotropy with hexane. After adding water to the reaction system to deactivate the catalyst, vacuum distillation was performed, and 160 g of secondary butyl α-hydroxyisobutyrate (GC purity: 99.6%) was obtained as a fraction at 78 mmHg and 105 °C.

[0107] [Isobutyric acid ester compound having an alkenoyloxy group at the α-position] <Example 1: Synthesis and aroma evaluation of isopropyl α-methacryloyloxyisobutyrate> A 50 mL glass flask equipped with a stirrer, a condenser, and a dropping device was charged with 14.6 g of isopropyl α-hydroxyisobutyrate synthesized in Synthesis Example 1 and 58 mg of iron(III) chloride (manufactured by Alfa Aesar). While stirring at room temperature, 15.3 g of methacrylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly dropped. After completion of the dropping, the mixture was heated to 60 °C and stirring was continued for 12 hours. From the GC analysis of the reaction solution, it was confirmed that isopropyl α-methacryloyloxyisobutyrate was obtained at a reaction yield of 81.5% by the reaction of the following formula (6). Thereafter, washing operations were performed twice with a 10% aqueous sodium carbonate solution and once with a saturated aqueous sodium chloride solution, dried over magnesium sulfate, concentrated, and 12.0 g of isopropyl α-methacryloyloxyisobutyrate (GC purity: 98.3%) was obtained by silica gel column chromatography. The aroma evaluation of the obtained isopropyl α-methacryloyloxyisobutyrate was carried out by the method described below. The results of the aroma evaluation are shown in Table 1.

[0108] [Chemical formula]

[0109] <Examples 2 to 4: Synthesis and Aroma Evaluation of Various α-Alkenoyloxyisobutyric Acid Esters> Using the same reaction apparatus as in Example 1, α-hydroxyisobutyric acid ester (isopropyl α-hydroxyisobutyrate synthesized in Synthesis Example 1 or secondary butyl α-hydroxyisobutyrate synthesized in Synthesis Example 2), iron(III) chloride (manufactured by Alfa Aesar) was used at 0.03 mol% with respect to each α-hydroxyisobutyric acid ester, and various acid anhydrides corresponding to the resulting α-alkenoyloxyisobutyric acid esters were used at 1 equivalent with respect to each α-hydroxyisobutyric acid ester for the reaction. The operation was the same as in Example 1, and various α-alkenoyloxyisobutyric acid esters were obtained by silica gel column chromatography. The GC purity, stereoisomer ratio (hereinafter referred to as E / Z ratio), results of NMR spectrum analysis, and results of GC-MS analysis of the obtained various α-alkenoyloxyisobutyric acid esters are shown below. For compounds containing stereoisomers, the results of NMR spectrum analysis and GC-MS analysis of the E isomer are described. In addition, the aroma evaluation of the obtained various α-alkenoyloxyisobutyric acid esters was carried out by the method described later. The results of the aroma evaluation are shown in Table 1.

[0110] 〔Secondary Butyl α-Methacryloyloxyisobutyrate〕 GC purity 99.6%

[0111] 〔Isopropyl α-2-Butenoyloxyisobutyrate〕 GC purity 99.4% (E / Z = 99 / 1) 1 H NMR (500 MHz, CDCl3) δ1.224 (6H, d, J = 6.5Hz), 1.551 (6H,s), 1.880 (3H, dd, J = 6.5, 1.5Hz), 5.040 (1H, sept, J = 6.5Hz), 5.846 (1H, dq, J = 15.5, 1.5Hz), 6.970 (1H, dq, J = 15.5, 6.5Hz) 1313C NMR (125 MHz, CDCl3) δ17.92, 21.50, 24.51, 68.53, 77.93, 122.57, 145.04, 165.13, 172.09 Exact.Mass 215.12900 (C 11 H 18 O4, parent peak)

[0112] [α-2-Butenoyloxyisobutyric acid secondary butyl] GC purity 99.6% (E / Z = 98 / 2) 1 1H NMR (500 MHz, CDCl3) δ0.837 - 0.932 (3H, m), 1.194 (3H, d, J = 6.5Hz), 1.537 - 1.601 (2H, m), 1.556 (3H, s), 1.558 (3H, s), 1.879 (3H, dd, J = 7.0, 1.5Hz), 4.872 (1H, sext, J = 6.5Hz), 5.846 (1H, dq, J = 15.5, 1.5), 6.970 (1H, dq, J = 15.5, 7.0) 13 13C NMR (125 MHz, CDCl3) δ9.53, 17.94, 19.12, 24.57, 24.62, 28.61, 73.14, 78.02, 122.59, 145.09, 165.14, 172.26 Exact.Mass 229.14347 (C 12 H 20 O4, parent peak)

[0113] [Example 5: Synthesis and aroma evaluation of isopropyl α-(3-methyl-2-butenoyloxy)isobutyric acid] A 100 mL glass flask equipped with a stirring bar, distillation head, and condenser was packed with 8.0 g of acetic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 23.5 g of 3-methylcrotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). Under reduced pressure, the mixture was heated and stirred at 90°C and 30-60 hPa for 10 hours, removing the resulting acetic acid from the top of the column, to prepare 3-methylcrotonic anhydride. The mixture was allowed to cool to 60°C, and 14.3 mg of iron(III) chloride (manufactured by Alfa Aesar) dissolved in 11.4 g of isopropyl α-hydroxyisobutyrate synthesized in Synthesis Example 1 was slowly added dropwise. The mixture was heated at 60°C for 3 hours under normal pressure (atmospheric pressure), and isopropyl α-(3-methyl-2-butenoyloxy)isobutyrate was obtained with a reaction yield of 88%. Subsequently, the solution was washed twice with a 10% sodium carbonate aqueous solution and once with a saturated sodium chloride aqueous solution. After drying with magnesium sulfate, it was concentrated, and 10.0 g of isopropyl α-(3-methyl-2-butenoyloxy)isobutyrate (GC purity: 99.9%) was obtained by silica gel column chromatography. The results of the NMR spectral analysis and GC-MS analysis of the obtained isopropyl α-(3-methyl-2-butenoyloxy)isobutyrate are shown below. Furthermore, the aroma of the obtained isopropyl α-(3-methyl-2-butenoyloxy)isobutyrate was evaluated by the method described later. The results of the aroma evaluation are shown in Table 1.

[0114] 1 H NMR (500 MHz, CDCl3) δ1.225 (6H, d, J = 6.5Hz), 1.549 (6H, s), 1.893 (3H, d, J = 1.5Hz), 2.135 (3H, d, J = 1.5Hz), 5.054 (1H, sept, J = 6.5Hz), 5.688 (1H, sept, J = 1.5Hz) 13 C NMR (125 MHz, CDCl3) δ20.08, 21.52, 24.59, 27.33, 68.37, 77.38, 115.83, 157.20, 165.27, 172.36 Exact.Mass 229.14423 (C 12 H 20 O4, Parent Peak)

[0115] <Examples 6 and 7: Synthesis and Aroma Evaluation of Various Isopropyl α-Alkenoyloxyisobutyrates> Using the same reaction apparatus as in Example 5, acetic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), isopropyl α-hydroxyisobutyrate prepared in Synthesis Example 1, and pentenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) or tigric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), which are acid compounds corresponding to the obtained isopropyl α-alkenoyloxyisobutyrate, were used in 3 equivalents relative to isopropyl α-hydroxyisobutyrate. Iron(III) chloride (manufactured by Alfa Aesar) was used at 0.05 mol% in Example 6 and 0.1 mol% in Example 7 relative to isopropyl α-hydroxyisobutyrate. The reaction was carried out in the same manner as in Example 5, and various isopropyl α-alkenoyloxyisobutyrate compounds were obtained by silica gel column chromatography. The GC purity, E / Z ratio, NMR spectral analysis results of the E-isomer, and GC-MS analysis results of the E-isomer of the obtained isopropyl α-alkenoyloxyisobutyrate compounds are shown below. Furthermore, the aroma of the obtained isopropyl α-alkenoyloxyisobutyrate compounds was evaluated by the method described later. The results of the aroma evaluation are shown in Table 1.

[0116] [α-2-pentenoyloxyisobutyrate isopropyl] GC purity: 99.7% (E / Z=98 / 2) 1 H NMR (500 MHz, CDCl3) δ1.074 (3H, t, J = 7.5Hz), 1.228 (6H, d, J = 6.5Hz), 1.55 (6H, s), 2.202-2.247 (2H, m), 5.045 (1H, sept, J = 6.5Hz), 5.819 (1H, dt, J = 15.5, 1.5), 7.022 (1H, dt, J = 15.5, 6.5Hz) 13 C NMR (125 MHz, CDCl3) δ12.00, 21.53, 24.53, 25.26, 68.56, 77.96, 120.13, 151.27, 165.45, 172.13 Exact.Mass 229.14404 (C 12 H 20 O4, Parent Peak)

[0117] [α-2-methyl-2-butenoyloxyisobutyrate isopropyl] GC purity: 99.6% (E / Z=99 / 1) 1 H NMR (500 MHz, CDCl3) δ1.220 (6H, d, J = 6.5Hz), 1.565 (3H, s), 1.568 (3H, s), 1.792 (3H, dq, J = 7.0, 1.0Hz), 1.817-1.822 (3H, m), 5.041 (1H, sept, J = 6.5Hz), 6.857 (1H, qq, J = 7.0, 1.5Hz) 13 C NMR (125 MHz, CDCl3) δ11.87, 14.30, 21.51, 24.50, 68.43, 77.91, 128.55, 137.41, 166.78, 172.22 Exact.Mass 229.14414 (C 12 H 20 O4, Parent Peak)

[0118] <Example 8: Synthesis and aroma evaluation of isopropyl α-2-butenoyloxyisobutyrate> A 100 mL glass flask equipped with a stirring bar was packed with 3.98 g of 2-butic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 20 mL of diethyl ether (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.99 g of 5% palladium / barium sulfate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.18 mL of quinoline (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The mixture was stirred under a hydrogen atmosphere at room temperature (25°C) for 1.5 hours. After filtering the reaction mixture to remove the catalyst, the filtrate was concentrated and purified by silica gel column chromatography to obtain 1.96 g of a mixture of 84.1% 2-butenic acid (E / Z=3 / 97) and 15.9% butanoic acid. 1.82 g of the above mixture containing 2-butenoic acid and 3.75 g of thionyl chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were packed into a 100 mL glass flask equipped with a stirring bar, and the mixture was stirred at 50°C for 2 hours. After concentrating the reaction mixture to remove unreacted thionyl chloride, 3.11 g of isopropyl α-hydroxyisobutyrate synthesized in Synthesis Example 1 was added, and the mixture was stirred at room temperature for 16 hours. Subsequently, the mixture was dissolved in hexane, washed four times with 15% aqueous sodium carbonate solution, dried over magnesium sulfate, concentrated, and purified by silica gel column chromatography to obtain 1.02 g of a mixture of isopropyl α-2-butenoyloxyisobutyrate (GC purity: 81.4% (E / Z = 29 / 71)) and isopropyl α-butanoyloxyisobutyrate (GC purity: 17.5%). The results of the NMR spectral analysis of the Z-isomer and the GC-MS analysis of the Z-isomer of the obtained isopropyl α-2-butenoyloxyisobutyrate are shown below. Furthermore, the aroma of the obtained isopropyl α-2-butenoyloxyisobutyrate was evaluated using the method described below. The results of the aroma evaluation are shown in Table 1.

[0119] 1 H NMR (500 MHz, CDCl3) δ1.230 (6H, d, J = 6.0Hz), 1.568 (6H,s), 2.117 (3H, dd, J = 7.3, 1.8Hz), 5.057 (1H, sept, J = 6.0Hz), 5.798 (1H, dq, J = 11.5, 1.8Hz), 6.344 (1H, dq, J = 11.5, 7.3Hz) 13 C NMR (125 MHz, CDCl3) δ15.31, 21.58, 24.63, 68.55, 77.89, 120.52, 145.50, 165.21, 172.04 Exact.Mass 215.12853 (C 11 H 18 O4, Parent Peak)

[0120] [Fragrance evaluation] The results of evaluating the aroma of the isobutyrate compounds having an alkenoyloxy group at the α-position obtained in Examples 1 to 8 by a perfumer are shown in Table 1.

[0121] [Table 1] (In the structural formulas of Examples 3, 4, 6, 7, and 8, the carbon-carbon double bond represented by the crossed double line indicates both the trans form (E form) and the cis form (Z form) of the stereoisomers generated by that double bond.)

[0122] [Fragrance composition] <Example 9: Fruity herbal type fragrance composition> A fragrance composition was prepared by adding 35 parts by mass of isopropyl α-methacryloyloxyisobutyrate obtained in Example 1 to 965 parts by mass of a fragrance composition having the composition shown in Table 2. By aroma evaluation by a perfumer, adding isopropyl α-methacryloyloxyisobutyrate of Example 1 to the fragrance composition having the composition described in Table 2 could impart a strong green feeling and a fruity feeling. As a result, a fruity herbal type fragrance composition that can be used in household products such as cleaners was obtained.

[0123] [Table 2]

[0124] <Example 10: Natural essential oil-like magnolia type fragrance composition> A fragrance composition was prepared by adding 100 parts by mass of isopropyl α-2-methyl-2-butenoyloxyisobutyrate obtained in Example 7 to 900 parts by mass of a fragrance composition having the composition shown in Table 3. Fragrance evaluation by a perfumer revealed that adding isopropyl α-2-methyl-2-butenoyloxyisobutyrate from Example 7 to the fragrance composition with the composition described in Table 3 improved the diffusion of the fragrance, resulting in a blended fragrance with a broader top note. As a result, a natural essential oil-like magnolia-type fragrance composition that can be used as a base fragrance with a natural image was obtained.

[0125] [Table 3]

[0126] The results of the examples show that the isobutyric acid ester compound having an alkenoyloxy group at the α-position of the present invention has a complex fragrance of floral and other aromas. Therefore, it is possible to obtain a fragrance composition containing an isobutyric acid ester compound useful as a fragrance as an active ingredient, which provides not only the aforementioned fragrance but also increased fragrance strength and diffusivity. Therefore, the isobutyric acid ester compound having an alkenoyloxy group at the α-position of the present invention is useful as an active ingredient in fragrance compositions, and the resulting fragrance composition can exhibit desired fragrance properties when incorporated into various products. Furthermore, the isobutyric acid ester compounds having an alkenoyloxy group at the α-position of the present invention are useful as fragrances because they possess a complex aroma of floral and other fragrances. The isobutyric acid ester compounds having an alkenoyloxy group at the α-position of the present invention have a floral aroma, but in addition, depending on the differences in the unsaturated hydrocarbon group and alkyl group, they also exhibit aromas such as green, rose, herbal, woody, balsamic, and fruity. Therefore, the isobutyric acid ester compounds having an alkenoyloxy group at the α-position of the present invention are useful as fragrances and can be suitably used as fragrances.

Claims

1. A fragrance composition containing a compound represented by the following formula (1) as an active ingredient. 【Chemistry 1】 (In formula (1), R 1 R is a linear or branched olefinic unsaturated hydrocarbon group having 2 to 4 carbon atoms, 2 (These are linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms.)

2. In formula (1), R 1 The fragrance composition according to claim 1, wherein is a linear or branched olefinic unsaturated hydrocarbon group having 3 to 4 carbon atoms.

3. In formula (1), R 1 The fragrance composition according to claim 1 or 2, wherein is an isopropenyl group.

4. In formula (1), R 2 The fragrance composition according to claim 1 or 2, wherein is a branched alkyl group having 3 to 4 carbon atoms.

5. In formula (1), R 2 The fragrance composition according to claim 1 or 2, wherein is an isopropyl group or a secondary butyl group.

6. In formula (1), R 2 The fragrance composition according to claim 1 or 2, wherein is an isopropyl group.

7. In formula (1), R 1 is an isopropenyl group and R 2 is an isopropyl group, R 1 is an isopropenyl group and R 2 is a secondary butyl group, R 1 is a 1-propenyl group and R 2 is an isopropyl group, R 1 is a 1-propenyl group and R 2 is a secondary butyl group, R 1 is a 1-butenyl group and R 2 is an isopropyl group, R 1 is a 1-methyl-1-propenyl group and R 2 is an isopropyl group, or R 1 is a 2-methyl-1-propenyl group and R 2 is an isopropyl group, the perfume composition according to claim 1.

8. Use of the compound represented by the following formula (1) as a fragrance. 【Chemistry 2】 (In formula (1), R 1 R is a linear or branched olefinic unsaturated hydrocarbon group having 2 to 4 carbon atoms, 2 (These are linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms.)

9. A compound represented by the following formula (2). 【Transformation 3】 (In formula (2), R 3 R is a linear or branched olefinic unsaturated hydrocarbon group having 3 to 4 carbon atoms, 4 R is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. 3 (Excluding the isopropenyl group.)

10. In formula (2), R 4 The compound according to claim 9, wherein is a branched alkyl group having 3 to 4 carbon atoms.

11. In formula (2), R 4 The compound according to claim 9 or 10, wherein is an isopropyl group or a secondary butyl group.

12. In formula (2), R 4 The compound according to claim 9 or 10, wherein is an isopropyl group.

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